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By E. P. Palmatier

RECENTLY a cooling system has been in process of installation on the 3400 and 3600-ft. levels of the Magma copper mine at Superior, Ariz. The general system of ventilation employed at this inclined-vein mine is as follows: Ventilating air enters the shafts on the western side of the mine. Booster fans at each level each deliver approximately 38,000 cu. ft. per 'min. to the drifts. This air passes diagonally upward to the upper levels of the mine on the eastern side, where it passes up the shafts to large exhaust fans on the surface. Owing to the dip of the vein, all operations on the eastern side of the mine are above the 2500-ft. level, and those on the western side below the 2500-ft. level. At present, 2500 lineal feet of new drifts are being driven-on each of the 3400 and 3600 levels. The rock temperature is about 135°F. Until the new installation is completed, ventilating air for the two levels is supplied through Flexoid tubing from small booster fans -on the 3200-ft. level. The air picked up by these booster fans has a dry-bulb temperature of approximately 85°F. and a wet-bulb temperature of 82°F. By the time this air reaches the end of the Flexoid tubing at the 3600-ft. level, the dry-bulb rises to 101°F. and the wet-bulb to 86°F. The conditions at the head of the new drift were 102' dry-bulb and 93' wet-bulb.

Jan 1, 1937

By Thos Gibson

THE object of taxation is the raising of a revenue. Unless a tax accomplishes this, it is a failure. The right to take for public purposes a part of the moneys obtained from the carrying on of private enterprises is an attribute possessed only by a lawful government, and may indeed he called the supreme attribute of government. In free, democratic communities this power must of necessity rest upon the consent of the governed. Power implies obligation, hence it is obviously the duty of a government, in framing a system of taxation, to provide one which, while effective in producing a revenue, is also just and impartial. It will be conceded that mines and mining property ought to bear a fair share of the public expenditure. The question is, upon what basis taxation should proceed. Two separate taxing principles are usually contended for: Taxation should be proportionate to the benefits received by the person or property taxed; taxation should be based on ability to pay. A third is sometimes added, taxation should have reference to the extent and value of the natural resources enjoyed. As applied to mining taxation, it is pointed out by those who support the first mentioned basis that, mines being usually situated in rocky and hence sparsely peopled regions, mining companies are frequently obliged to construct roads, railways, telegraph and telephone lines, schools, water and sewerage systems, and many other amenities and conveniences of civilization, the cost of which in regions better suited for agriculture and consequently more thickly populated, has either been defrayed locally, or can be spread over a sufficiently large taxable group of people to materially lighten the financial burden on the mine. The mining com¬pany, it is argued, having made these outlays, should receive credit for, them and be relieved of taxation to a corresponding extent. There may be some force in this contention, but the situation is capable of relief without attempting to place taxation upon so unworkable a basis as the value of benefits received. Who is to be the judge of these benefits, and how are they to be valued? The very existence of a mining company and its ability to carry on business in peace and security, depend on the prevalence of law and order, which is a result of good government. The state provides protection against violence, and courts of law for

Jan 4, 1919

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined for the system gadolinium-nickel. Nine intermetallic compounds have been found at compositions corresponding to the following gadolinium-nickel ratios: 3:1, 3:2, 1:1, 1:2, 1:3, 2:7, 1:4, 1:5, 2:17. The GdNi and GdNi5 compounds have congruent melting points of 1300' and 1500°C, respectively while the remaining compounds melt in-congruently. Eutectics exist at 15 wt pct Ni, 31 1/2 wt pct Ni and 87 wt pct Ni with melting points of 6703 8803 and 1220°C, respectively. IN a continuing investigation of the properties of rare earth alloys, a study has been made of the gadolinium-nickel system. Previous work encompassed the iron containing alloys and a subsequent paper will deal with the constitution of the gadolinium-cobalt system. Vogel,1 examined alloys of nickel with lanthanum and cerium. R3Ni, RNi, RNi2, RNi3, RNi4, and RNi5 compounds were found. Endter and Klemm,2 Fulling et al.3 Heumann,4 and Nowotny5 found the 1:2 compositions of this series to exist in a C-15 (face-centered cubic) structure, and the 1:5 compositions in a hexagonal system. Jepson and Duwez6 more recently examined these 1:2 and 1:5 compositions and generally confirmed earlier data while Wernick and Geller7 most recently have given additional data on the GdNi5 compound. Comparisons with our results will be made in the appropriate section of this report. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been given in our earlier paper.8 Chemical analyses of the alloy samples were made by dissolving the specimen in nitric acid, precipitating the gadolinium as hydroxide and the nickel with dimethylglyoxime. Both precipitates were ignited to oxide and weighed. RESULTS Microstructure— Metallography of alloy specimens in this series has been conducted on both arc-melted and annealed materials. Etchants used have been 5 pct nital with approximately 10 pct distilled water added, for high gadolinium samples; Carapella's ferric chloride solution for intermediate compositions; and Marble's (copper sulfate) reagent for high nickel content alloys. Because of difficulties encountered in the grinding and polishing of specimens containing 40 to 75 wt pct Ni, no photomicrographs were made of such specimens. The microstructure of an arc-melted 5.3 wt pct Ni alloy is shown in Fig. 1. Light etching primary grains of gadolinium are embedded in an eutectic matrix. The microstructure of an alloy of 9.55 wt pct Ni alloy, Fig. 2, annealed 50 hr at 700°C, consists almost entirely of the intermetallic compound Gd3Ni. The structure of an arc metal alloy of approximately 19 pct Ni, Fig. 3, consists of grains of the compound GdNi embedded in the Gd3Ni2-Gd3Ni eutectic. The arc-cast structure of the 38.7 wt pct Ni alloy is shown in Fig. 4. Large primary grains of a compound rest in a matrix structure of coarse GdNi-GdNiz eutectic. Because of the occurrence of several peritectic compounds in the central region of the diagram, identification of the primary structure in this alloy is not certain. As has been indicated above, microstructures of alloy specimens containing between ca 40 and 75 wt pct Ni have not been photographed. These specimens were highly brittle, and macro- and micro-cracking were impossible to control in the grinding and polishing procedures. Prolonged annealing did not alleviate this condition. Visual observations in small specimens did, however, provide evidence for a multiplicity of phases and peritectic dissociations of compounds although rationalization of structures was not possible.

Jan 1, 1962

By Dodge, C. E.

ONE of the first mining areas to be developed in Arizona was that in the district centering about Clifton and Morenci. Traces of metals were first noticed by Henry Clifton on an expedition in 1864. Definite copper outcroppings were also reported in the following year by General J. H. Carleton when he led his troops into the district on an Indian raid. Actual mining operations were started in the early seventies. and the first smelter was finished in 1873. Two adequately financed companies acquired most of the property, and both commenced production about 1882. These were the Arizona Copper Co.. owned by a group of Scotch investors, and the Detroit Copper Mining Co., afterwards purchased by the firm of Phelps, Dodge & Co. Later the Shannon Copper Co. acquired and operated a number of claims in the northern part of the district. These three companies all operated underground, mines independently for many years.

Jan 1, 1942

Since production curtailment for other than engineering reasons is gradually disappearing, and more and more wells are now producing at capacity and showing declining production rates, it was considered timely to present a brief review of the development of decline-curve analysis during the past three or four decades. Several of the commoner types of decline curves were discussed in detail and the mathematical relationships between production rate, time, cumulative production and decline percentage for each case were studied. The well-known loss-ratio method was found to be an extremely valuable tool for statistical analysis and extrapolation of various types of curves. A tentative classification of decline curves, based on their loss ratios, was suggested. Some new graphical methods were introduced to facilitate estimation of the future life and the future production of producing properties where curves are plotted on semilogarithmic paper. To facilitate graphical extrapolation of hyperbolic-type decline curves, a series of decline charts was proposed, which will make straight-line extrapolation of both rate-time and rate-cumulative curves possible. Introduction During the period of severe production curtailment, which is now behind us, production-decline curves lost most of their usefulness and popularity in prorated areas because the production rates of all wells, except those in the stripper class, were constant or almost constant. While production-decline curves were thus losing in importance for estimating reserves, an increasing reservoir consciousness and a better understanding of reservoir performance developed among petroleum engineers. This fact, together with intelligent interpretation and use of electric logs, core-analysis data, bottom-hole pressure behavior and physical characteristics of reservoir fluids, eliminated a considerable part of the guesswork in previous volumetric methods and put reserve estimates, based on this method, on a sound scientific basis' At the same time, a number of ingenious substitutes were developed for the regular production-decline curve, which made it possible to obtain an independent check on volumetric estimates in appraisal work, even though the production rates were constant. with the now steadily increasing demand for oil to supply the huge requirements of this global war, proration for reasons of than prevention of underground waste is gradually disappearing. More and more wells are, or will be, producing at capacity or at their optimum rates, as determined by sound engineering practice. With this trend, the character of producing wells seems to regain, more or less, its "individuality," and the old and familiar decline curve appears to have had a comeback as a valuable tool in the hands of the petroleum engineer. It may be timely, therefore, to retrace the development of decline-curve analysis in the past by presenting a brief chronological review of bulletins and papers published during the past three or four decades, which have

Jan 1, 1945

By L. D. Jaffe

From data found in the literature, a method has been derived for calculating hardenability of titanium alloys from their composition. A single graph gives the contributions of each alloying element. These are simply added to a base hardenability for unalloyed titanium. Results agree satisfactorily with measured harden-abilities. RECENTLY the importance of hardenability of titanium alloys in permitting attainment of high strength and hardness has become apparent. If a titanium-base alloy has adequate hardenability for the section size and quenching practice used, it can generally be heat treated to high strength and hardness either by simple quenching or cooling from temperatures near the ß transus, by quenching and tempering (aging), or perhaps by direct isothermal transformation of ß1,2 If the hardenability is inadequate, high strength cannot be attained. Preliminary charts translating hardenability requirements for shapes quenched in various media into terms of Jominy end quenched hardenability specimens or ideal round sizes are now available for titanium alloys." The method proposed in 1942 by M. A. Grossmann for calculating hardenability of steels from composition has proved to be of great practical value.' It appeared worthwhile to see whether, using information available in the literature, a corresponding method for calculating hardenability of titanium-base alloys could be derived. Data No systematic experimental study of the hardenability of titanium-base alloys has yet been made. There is available, however, a considerable quantity of scattered data bearing on hardenability. Some investigators determined Jominy curves on one or several alloys. Others reported as-quenched hardness for specimens of a few alloys cooled at various rates or in various media. Still others gave the as-quenched hardness for systematically varied composition, using one or several cooling mediums. The measurements utilized in this work were limited to hardness. Strength measurements were not used because a low strength may reflect high hardness combined with brittleness. Since, in general, the hardness of titanium alloys goes through a peak as the cooling rate is varied from extremely fast to extremely slow, the cooling conditions at which peak hardness was found were taken as the measure of hardenability.1,2 When as-quenched hardness was found to drop as the content of an alloying element (believed to increase hardenability) was raised, this was taken as an indication that the cooling rate was faster than that giving peak hardness; otherwise, the hardness should go up because of solid solution hardening. Also, if the hardness increased on tempering at low temperatures, this was again taken to indicate that the cooling rate had been faster than that giving peak hardness. Many of the data did not indicate precisely the cooling conditions for peak hardness but merely set a maximum or a minimum bound, or a bracket. Since the sizes of specimens quenched and the location of the hardness readings were not always given, it was occasionally necessary to estimate reasonable limits for them. Only the nominal compositions were available in some cases. As quenching from below the ß transus is equivalent to starting with a mixture of a and ß phases, whose individual composition would differ from the overall composition of the alloy, only measurements after quenches from above the ß transus were used. Hardness measurements on samples heated during metal-lographic mounting were also discarded. Because of their bulk, the data used will not be reproduced. They have been or will be published elsewhere.5-22 Approach All data were first translated into terms of ideal round size. For conversion from Jominy or quenched round or sheet, the author's graphs were used." For a few furnace cools or helium quenches where cooling rates were given, conversion was made on the basis of equal cooling coefficient.23 Plots of ideal round size for peak hardness against percentage of alloying element were next made for

Jan 1, 1956

By W. Armstrong Price

INVESTIGATION by German chemists during the World War showed that particles of iron oxide form rapidly in iron pipes carrying hydrogen gas under pressure when the gas contains small amounts of water. Under these conditions, the gas frequently exploded when expanding into a dirigible. The explanation of the explosions lies in the building up of a charge of static electricity in the flow just beyond the orifice and the ignition of the gas by a spark accompanying discharge of the electricity. Friction between the moving particles and the pipe generated the electric charge, which was manifested by a pale blue glow formed in the flow at pressures above two atmospheres. In one experiment, this glow, at eighty atmospheres, extended for a distance of forty to fifty centimetres, but did not ignite hydrogen and air mixtures until the charge was col-lected by a conductor and discharged across a gap between electrodes placed at the side of the column of gas. Autoignition did not occur when this discharge was effected at a distance from the gas column, nor if the gas used was thoroughly dried and free from impurities. The electric charge has been studied by placing various wire and screen conductors in the outcoming stream of gas, Guest having summarized these experiments. The application of these conclusions to fires in petroleum and natural gas issuing uncontrolled from wells is made in the following paper, citing the ignition of a wild gas well in Texas.

Jan 1, 1936

By F. B. Plummer

PETROLEUM ENGINEERING deals with the production, transportation, and refining of crude oil. Refining is chiefly the work of the chemical engineer; production, that of the petroleum engineer. Production engineering only is discussed in this paper. Petroleum production engineering is closest related to and, in fact, is a branch of mining engineering. Formerly, many petroleum engineers were trained as mining engineers or mining geologists. The profession is related also to mechanical and civil engineering to about the same extent that mining engineering is. Petroleum production draws upon the mechanical branch for drilling and pumping machinery and upon civil engineering for the construction of transportation lines, water supplies, and water-disposal plants. Fundamentally, petroleum production engineering deals with the removal of the oil from the reservoir rocks, just as mining is concerned with the removal of ore. The process of oil production demands a specialized knowledge just as distinct from mechanical and civil engineering as mining is distinct from operating a Diesel engine. Even though the chief tools of the petroleum engineer are the drill and the pump, these may be of little avail, and certainly not efficient, if their selection and use is not based on a knowledge of the physical chemistry of oil, the geology of the formations, the structure of the oil sand, the hydrodynamics of the reservoir, and the interrelation of all these many factors.

Jan 1, 1936

By Gilbert Soler

PRODUCERS of alloy steels recognize the importance of chemical composition in rela-tion to the hot-working properties and the typical surface defects found in their prod-uct. Each analysis of steel has its own peculiar characteristics. Under conditions of standard mill practice each analysis is susceptible to certain types of defects. Mill practice must be varied to obtain the best combination of surface and internal quality in the product. Chemical composition influences the cast structure and crystallization character-istics of the ingot. It also determines the rate of heating and cooling, the plastic hot-working range, and the phase structure of the steel at various temperatures as well as the tendency toward scale formation and decarburization, This paper endeavors to emphasize the manner in which chemical composition affects the various properties of steel, and to indicate the relative impor-tance of these factors in relation to the hot-working properties and surface charac-teristics of killed steel. The influence of chemical composition may be outlined as follows: I. Effect on the cast structure of steel, including: A. State of deoxidation, and type of inclusions. B. Gas content of steel. C. Freezing point and melting point of steel.

Jan 1, 1940

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS ?ARE ASSOCIATES. THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. *AARONS, J. BOYD, Vivian Gold Mining Co., Ltd., Harris, West. Australia. '05 *ABADIE, EMILE R., Cons. and Min. Engr., 214 Union Savings Bank Bldg., Oakland, Cal. '76 ?ABBÉ, MAX F., Prest., Abbé Engineering Co, 220 Broadway, New York, N.Y. '07 *ABBOTT, CHARLES W., Min. Engr. Pioche, Nev. ?08 *ABBOTT, JAMES W., Min. Engr: Ploche, Lincoln Co., Nev. '94

Jan 1, 1917

By E. L. BROKENSHIRE

FLUORSPAR, a little known non-metallic mineral, referred to technically as fluorite, chemically as calcium fluoride, is a compound of calcium and fluorine in the ratio of one molecule of calcium to two of fluorine. By weight it is composed of 51.3 per cent of calcium and 48.7 per cent of fluorine. Its specific gravity is 3.2. It is brittle, has a hardness of four and can be easily scratched with a knife. It weighs about 200 Ib. per cubic foot and has a melting point of 1650" F. The color of fluorspar ranges from pure white and opaque white, according to its purity, to various hues of yellow, green, pink, lavender, blue and brown, to bluish black. Although the lumps have color, when ground the fluorspar becomes pure white. The reason for this is because the mineral usually carries no fixed pigment, the color being produced by the re- fraction of light rays within the crystal structure and small quantities of organic matter which readily oxidizes. It crystallizes in the isometric system with perfect octahedral cleavages.

Jan 1, 1929

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments. Survey: The pebble rock phosphate mining and washing operations in Florida (fig. 1) are along the river basins of the Alafia to the west and the Peace to the east. The elevation of the area varies between 40 and 170 ft above sea level. Effluents from the operations find their way into one of the two river systems (fig. 2), the Peace River which flows into Charlotte Harbor and the Alafia into Tampa Bay, both along the Gulf of Mexico. There are no major industries along these rivers below the phosphate operations. On the Peace River, the town of Arcadia, approximately 50 miles below the phosphate operations, obtains its water from the river. No other communities along the rivers use them as a source of water supply. Small communities, farms, and ranches are located along the rivers and both rivers drain vast swamp areas. Complaints had been received at the office of the Chief Sanitary Engineer, of the Florida State Board of Health,' that both rivers were turbid at various times and that fishing in the Alafia River was "not as good as it used to be." Tests made by another agency on the dissolved oxygen content of the Alafia River revealed that the oxygen content, at times, was comparatively low.= However, it was not shown that the phosphate wastes had any effect upon the oxygen content of the stream. The river waters are normally brown in color due to drainage from vast swamp areas and are very shallow, from 2 to 6 ft in depth. Turbid waters have been noted in streams coming from the present phosphate operations and also from streams along which there are no operations at the present time. It was learned from "old timers" that, when many more companies than at present were operating along both the Alafia and Peace Rivers forty or fifty years ago, no attention was paid to prohibiting the disposal of slimes along the river basins. During dry periods now in some of the river swamps where drainage ditches have been dug, it is indicated clearly that phosphate slimes were disposed of directly into the river swamps for many years past. Places have been observed where there were alternating strata of phosphate mud, leaf mold, and quartz sand. The former practice of indiscriminate disposal of wastes accounts for some turbidity, particularly after heavy rains and washouts and during clearing of land and digging of drainage ditches. During a six months' period in which a large tract of land was being cleared and drainage ditches dug, a small stream (Six Mile Creek), which previously had been clear, showed a turbidity of 600 ppm and remained turbid until the clearing was completed; after which the stream again flowed clear. An interview with the operator of the municipal water plant, which is about 50 miles below the phosphate operations on the Peace River and which used this river as a source of supply, revealed that there had been no taste in the water for the past ten years, other than that occasionally encountered from increased growth of algae. The operations of each of the cooperating com-

Jan 1, 1951

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments. Survey: The pebble rock phosphate mining and washing operations in Florida (fig. 1) are along the river basins of the Alafia to the west and the Peace to the east. The elevation of the area varies between 40 and 170 ft above sea level. Effluents from the operations find their way into one of the two river systems (fig. 2), the Peace River which flows into Charlotte Harbor and the Alafia into Tampa Bay, both along the Gulf of Mexico. There are no major industries along these rivers below the phosphate operations. On the Peace River, the town of Arcadia, approximately 50 miles below the phosphate operations, obtains its water from the river. No other communities along the rivers use them as a source of water supply. Small communities, farms, and ranches are located along the rivers and both rivers drain vast swamp areas. Complaints had been received at the office of the Chief Sanitary Engineer, of the Florida State Board of Health,' that both rivers were turbid at various times and that fishing in the Alafia River was "not as good as it used to be." Tests made by another agency on the dissolved oxygen content of the Alafia River revealed that the oxygen content, at times, was comparatively low.= However, it was not shown that the phosphate wastes had any effect upon the oxygen content of the stream. The river waters are normally brown in color due to drainage from vast swamp areas and are very shallow, from 2 to 6 ft in depth. Turbid waters have been noted in streams coming from the present phosphate operations and also from streams along which there are no operations at the present time. It was learned from "old timers" that, when many more companies than at present were operating along both the Alafia and Peace Rivers forty or fifty years ago, no attention was paid to prohibiting the disposal of slimes along the river basins. During dry periods now in some of the river swamps where drainage ditches have been dug, it is indicated clearly that phosphate slimes were disposed of directly into the river swamps for many years past. Places have been observed where there were alternating strata of phosphate mud, leaf mold, and quartz sand. The former practice of indiscriminate disposal of wastes accounts for some turbidity, particularly after heavy rains and washouts and during clearing of land and digging of drainage ditches. During a six months' period in which a large tract of land was being cleared and drainage ditches dug, a small stream (Six Mile Creek), which previously had been clear, showed a turbidity of 600 ppm and remained turbid until the clearing was completed; after which the stream again flowed clear. An interview with the operator of the municipal water plant, which is about 50 miles below the phosphate operations on the Peace River and which used this river as a source of supply, revealed that there had been no taste in the water for the past ten years, other than that occasionally encountered from increased growth of algae. The operations of each of the cooperating com-

Jan 1, 1951

By Ralph H. Sweetser

AT the joint session of Blast Furnace and Open Hearth Committees, April 7, 1937, at Birmingham, the subject of the quality of basic open-hearth pig iron was so well presented and discussed from so many different viewpoints that it was the general opinion that progress had been made and that such meetings were conducive to the advancement of the art of making pig iron of the right quality for the open-hearth man to produce the most satisfactory quality of steel. It was agreed that there is a decided differentiation between the chemical analysis of pig iron and the "quality" of pig iron. Paul J. McKim said that open-hearth furnace operators frequently make reference to certain types of iron as "bad iron," "dirty iron," "cold metal," etc., claiming that when using these irons, although they are within specified chemical analysis, it is impossible to produce quality steel. Mr. McKim gave a list of the suggested causes of those "certain types" of bad irons that have a thoroughly respectable analysis but a thoroughly disreputable character. Another open-hearth man, P. A. MacIsaac, of Nova Scotia, said that The effects of iron that is below standard in analysis or in that mysterious property called quality, are well known to all open-hearth operators. It has been shown that iron of this type results in the production of steels on which the rejections of finished product run high. What is to be done about it? I would say that the burden of producing high-quality iron should be placed squarely on the shoulders of the blast furnace man, even as that of making good steel is shouldered by the open-hearth man. It is the purpose of this paper to bring out into the open this "mysterious property called quality"; that is, in those "certain types" of basic pig iron that make it impossible to produce quality steels; and at the same time to point the way for the blast-furnace man to be able to shoulder the burden that Mr. MacIsaac and all other open-hearth men and foundry-men have placed upon him. Silicon, sulphur, phosphorus and manganese are not the guilty elements because these are known, specified and usually kept within the

Jan 1, 1938

By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick's second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method' are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5' could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5' or Ag'lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5' and 0.6 N HNO3 solution for the A"'), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5' atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By L. Leibowitz, M. G. Chasanov, L. W. Mishler

A drop calorimeter system is described for use in measuring enthalpies to 3600°K. Data are presented for tungsten between 2800" and 3600°K. The enthalpy of tungsten in cal per mole between 2000° and 3600°K can be represented by the equation HºT- Hº298 = - 1.7622 X 103 + 5.7772T + 8.9861 where T is in degrees Kelvin. A tabulation of com -puted values is presented for heat capacity, entropy, and free energy function. A drop calorimeter has been constructed to carry out enthalpy measurements at temperatures to 3600°K. Samples are heated by induction1 and dropped into a commercial adiabatic calorimeter, modified for this purpose. The experimental temperature is limited by the melting point of container materials and compatibility of the container and its contents. Several high-temperature drop calorimeters have been described in the literature1-5 but none has been used at temperatures as high as those in the present work; our measurements of the enthalpy of tungsten range from 2800" to 3600°K. DESCRIPTION OF EQUIPMENT An overall schematic view of the equipment is shown in Fig. 1. Power for the induction coil is supplied by a 25-kw 250 kHz Ther-Monic generator coupled to an iron core RF transformer. The Sample capsule is suspended in the work coil by 10-mil diam tungsten wires which are wrapped around a horizontal 5-mil diam tungsten wire. The horizontal suspension wire is clamped between two massive copper electrodes which are fixed in an x-y motion device that allows adjustment of the position of the heated capsule from outside the vacuum chamber. The copper electrodes are connected by flexible copper straps to a 1250-joule (5 kv, 100 pfarad) condenser bank. When it is desired to release the capsule, the condensers are discharged through the horizontal suspension wire causing it to vaporize rapidly. Very reliable and precise release of the capsule is achieved in this manner. Experiments have shown that no heat correction is required for this discharge energy. As part of the temperature measuring system, two prism holders have been incorporated in the apparatus. The upper prism holder is in the main vacuum chamber itself, whereas the lower one is in a side arm attached to the drop tube below the gate valve. The upper prism is mounted on a rotary vacuum feed-through, and may be moved under a protective shield when not in use. This prevents deposition of vapors on the prism surfaces when temperature measurements are not being made. Similarly, the lower prism is mounted on a push-pull vacuum feed-through, and when not in use may be pulled into its side tube. The prism mountings are fitted with guides and stops so that they may be moved precisely into the desired position. The aim throughout is to minimize the time the prisms are exposed to vapors from the hot samples. At the high temperatures reported in this paper, only the lower prism was used. The upper prism holder in these cases was fitted with an additional radiation shield. By using a prism and viewport, the lower surface of the samples can be observed by an optical pyrometer. The measurements discussed in this paper were obtained with a Leeds and Northrup 8622-C-S series manual pyrometer which is estimated to be accurate to 0.5 pct. Pyrometer calibrations and prism and window corrections were carried out in the conventional manner6 using tungsten strip lamps calibrated by the National Physical Laboratory, Teddington, England. Prism corrections were rechecked after each use. All work to date has been done in vacuum, and no measurable change has been observed in the prism correction below -2300°K for the upper prism and below -2800°K for the lower one. The total time of exposure of the prisms is about 50 sec per run. At high temperature, the final temperature reading is corrected by using the final A value for the prism; see Ref. 6 for details of this procedure. The calorimeter is a modified Parr Instrument Co. (Moline, lll.), Series 1230 adiabatic calorimeter with automatic jacket control. Other authors5 have used a similar calorimeter with good results. The calorimeter jacket cover and calorimeter cover are attached to the drop tube which contains a radiation shield. This shield is a gold-plated copper disc which can be operated manually from outside the calorimeter. The receiver is attached below the radiation shield and is lined with tungsten. In a typical experiment, the calorimeter and its jacket water temperatures were adjusted to 0.000°K temperature difference. The sample was allowed to equilibrate in the furnace at the desired temperature for about 20 min. The initial calorimeter temperature was then recorded, the sample dropped, and appropriate shutters closed. After about 3 min, the drop tube and receiver were filled with helium to 60 torr. The final calorimeter temperature was recorded after it had remained constant over a 5-min period. The equilibration time in the calorimeter was about 25 min. Thermistor probes are used to operate a hot and cold water supply system to maintain the jacket temperature equal to the calorimeter temperature. For actual measurements of the calorimeter temperatures, a quartz thermometer was used (Hewlett Packard Dymec Thermometer, Model #2801A). This thermome-

Jan 1, 1970

By Che-Yu Li, J. L. Gregg, W. F. Brehm

Oriented, oxygen-doped niobium bicrystals were tested in liquid lithium. The grain boundaries were attacked preferentially. The depth of the penetrated zone varies as (time)2. The penetration was aniso-tropic, had a high activation energy, and increased with the increased oxygen doping level. A possible model was proposed to account for the experimental observations. 1 HE grain boundary penetration of a metallic system by liquid metal has been studied by several investigators. Their results are summarized by Bishop.' Most of these works show that the penetration by liquid metal corresponds to the phenomenon of liquid metal wetting. In the case of a grain boundary, wetting will occur when twice the solid-liquid interfacial tension is smaller than the grain boundary tension resulting in the replacement of the grain boundary by two new solid-liquid interfaces. Other possibilities exist; for example, the atoms of the liquid metal may diffuse into the grain boundary region due to chemical potential gradient. The gradient can be produced by impurity segregation or simply be due to the increase in solubility in the grain boundary region. The penetrated grain boundary in these cases may remain solid at the test temperature. The Nb-Li system has been of considerable interest because of its possible technological applications. For fundamental interest it provides a possibility of studying the grain boundary penetration process which is not controlled by the wetting mechanism. The pure niobium is not attacked by the liquid lithium, but if niobium containing more than 300 to 500 ppm oxygen by weight is exposed to liquid lithium, corrosion occurs at the solid-liquid interface and preferentially at grain boundaries. Previous investigators2-' have proposed that this preferential corrosion at grain boundaries is caused by oxygen segregation there, with subsequent inward diffusion of lithium to form a Li-Nb-0 compound. These investigators also found that the corrosion could be retarded by adding 1 pct Zr to the niobium to precipitate the oxygen as ZrO2 upon proper heat treatment. However, there are no quantitative data on the kinetics of the grain boundary penetration process to test the validity of the proposed corrosion mechanism. In this work an investigation of this penetration process in oriented bicrystals was made as a function of the oxygen doping level in the bulk niobium and the grain boundary orientation. A possible model for the penetration process based on the experimental results was proposed. EXPERIMENTS Oriented niobium bicrystals were grown by arc-zone melting oriented single-crystal seeds.7 These bicrystals contained simple tilt boundary. The [001] directions in the two grains were tilted about a common [110]. The bicrystals were 31/2 in. long and 5 by 4 in. in cross section with the straight, symmetric, planar grain boundary longitudinally bisecting the crystal rod. The bicrystals were doped with oxygen by anodically depositing a layer of Nb2O on the surface in a 70 pct HNO solution at 100 v, using a stainless-steel cathode. The specimens were homogenized by annealing in evacuated quartz tubes at 127 5°C. Oxygen content of the niobium was measured from microhardness values, after DiStefano and Litmman.' Supplementary checks were made with vacuum-fusion analysis.7 Individual test specimens cut from the doped bi-crystal rods, about by by % in. in size, were tested inside double jacket sealed capsules. The inner jacket was niobium, the outer was stainless steel. The niobium inner jacket eliminated the problem of dissimilar-metal mass transfer.' The lithium (99.8 pct pure, obtained from Lithium Corp. of America) was handled only in a purified argon atmosphere in a Blickman stainless-steel glove box. After introduction of lithium, the capsules were sealed by welding. Further detailed experimental procedures are given in Ref. 7. The capsules were heat-treated in vertical Marshall resistance furnaces. Temperatures were controlled to When heating above 1100°C, it was necessary to seal the furnace work tube and flow argon through to prevent failure of the stainless-steel outer jacket of the capsule. Tests were made on 6" 2", 16" 2, and 33" i2" bicrystals at oxygen levels up to 2600 ppm by weight in the 6' and 16" crystals and with 1300 ppm oxygen in the 33' crystals. The oxygen levels were controlled to 100 ppm. Most of the quantitative data were obtained from 16" bicrystals between 800" and 1050°C. The capsules were quenched into water after the test and cut open with a water-cooled abrasive wheel. The capsules were then submerged in water, which dissolved the lithium and freed the specimen. Measurement of the depth of the penetrated zone in the grain boundary was done either on metallographically prepared surfaces or directly on the grain boundary plane after the specimen was fractured in tension in the grain boundary plane. The depth of penetration measured by both methods agreed well. Further details describing these techniques have been reported elsewhere.'p7

Jan 1, 1969

By A. E. Dwight, Paul A. Beck

Known CsCl-type phases in transition metal alloys are shown to be formed preferentially at an electron concentration of approximately 6; a tetragonally distorted version of the CsCl structure is stable at -e/a = 6.5. The relationship of the distortion to electron concentration is verified by experimental data for the quasibinary systems Time ,Os) , Ti(Re,Ir), and Ti(Re,Pt) and the ternary system Ti-Ru-Rh. It was noted some years ago1j2 that the occurrence of CsC1-type ordered structures in equiatomic binary alloys, AB, of transition metals correlates with the location of the component elements in the periodic table. One of the components, A, must be to the left and the other component. B, must be to the right of the chromium group. It was pointed out2 that the CsCl structure does not occur in CrFe. is metastable in VFe,3 and is stable in TiFe up to high temperatures, and that this progressively increasing stability may correspond to an increase in electron transfer between the two components and to a correlated decrease of the magnetic moment associated with the iron atoms. Such a decrease was in fact later demonstrated by Nevitt. 4 The binary CsC1-type phases that are formed by a transition metal with either another transition metal or a lanthanide are listed in Table I. Thirty-three of these phases occur at an average electron concentration (average number of electrons outside of closed shells) of e/a = 6. The five phases that are formed at an electron concentration of e/a = 5.5 appear to be borderline cases. This is suggested for instance by the fact that TiRe is bcc. without any long-range order, while TiTc (at the same electron concentration) has a CsCl ordered structure. Six of the undistorted CsCl phases formed by transition metals with one another have an average electron concentration of e/a = 6. 5. Table I. With the exception of Zr4,Rhs4 and Hf48Rh52. the B component in these phases is a first long-period transition metal, i.e.. iron or cobalt. TiNi. with an electron concentration of e/n = 7, appears to undergo transformation at around room temperature to a more complex ordered struct~re.~ The five other CsCl structures known to occur at e/a = 6.5 have either scandium or a lanthanide metal as the A component; the difference in the elec-tronegativity and in the e/a ratio between the component elements is in these phases very large, A(e/a) - 7, and they may be expected to have a rather strong ionic bond component. Presumably the ionic bond stabilizes the CsCl-type structure at the equiatomic composition and it overrides the electron concentration requirement. When the B element is not from the first long period and the A component is not a rare earth metal. equiatomic (AB) alloys of transition metals with an average electron concentration of e/a = 6.5 in most cases have a crystal structure closely related to the CsC1-type, but slightly distorted tetragonally, Table I. This was first found6 for VRu, NbRu. and TaRu. It was noted6 that the undistorted CsCl structure is also stable in the three systems. but at a lower electron concentration, near e/a = 6. In these systems this requires a deviation from equiatomic stoichiometry. which is otherwise ideally suited for the CsC1-type structure. A similar situation was later found in the Ti-Rh7 and the Ti-Ir systems. 8 The Ti-Rh alloys undergo a second distortion and become orthorhombic when the rhodium content becomes somewhat larger than 50 pct. As mentioned previously. TiRe does not have the CsC1-type ordered structure. In order to investigate how close TiRe is to the borderline of stability of the

Jan 1, 1970

By Murray F. Hawkins, W. J. Ainsworth

In all types of subsurface pressure gauges the extension which occurs in the pressure-sensitive element is a function of the difference between the external (well or calibration) pressure and the internal pressure within the gauge, rather than a function of the external pressure only. The internal pressure is near atmospheric and depends upon (a) the quantity of air sealed within the gauge at the time of calibration or measurement, (b) the quantity of moisture (liquid water), if any, sealed within the gauge, and (c) the temperature at which the calibration or well measurement is made. Part of this correction for the change of internal pressure with temperature is taken care of by the customary temperature coefficient of the gauge. However, part of it is not, and while this portion may be only a few psi, it is nevertheless predictable or preventable, and should be considered in precision measurements. ERROR NO. 1 If air is sealed in the gauge at the same temperature and pressure for both the calibration and the well measurements, the usual temperature correction will take care of any difference between calibration and well measurement temperatures. However, if air is sealed within the gauge at temperature T1 and pressure P1 at calibration but at temperature T2 and pressure P2 for a well measurement, because different amounts of air are sealed within the gauge in each case, the internal pressure at. or corrected to, calibration temperature Tr will he different by where all temperatures and pressures are absolute. The calibration temperature is used, and not the well measurement temperature, because the usual temperature correction reduces the well measurements to calibration temperature. The correction term as calculated by the above equation is separate from. and in addition to, the usual temperature correction. Example: T, = 540°R, sealing temperature at calibration P, = 14.7 psia, sealing pressure at calibration T2 = 460°R, sealing temperature at well P2 = 14.7 psia, sealing pressure at well Tr = 660°R, calibration temperature AP = 660 [14.7/460 — 14.7/540] = 3.1 psi While this error is small even under these somewhat maximal conditions, it nevertheless represents a practical situation which did occur, and which as a matter of fact gave rise to this note. Where AP is positive, as above, the correction is added to the measured pressure; where negative, subtracted from the measured pressure. This correction should also be considered in successive calibration runs where the gauge, for example, may be warm from a previous calibration at an elevated temperature. ERROR NO. 2 Where a small quantity of moisture (liquid water) is sealed within the gauge at atmospheric conditions, the increased vapor pressure of the water at higher well or calibration temperatures will cause an increase in internal pressure. This moisture will come presumably from condensation within the gauge following temperature changes, from moisture on the operator's hands, and from atmospheric moisture (rain, mist, fog, etc.). Calculation shows that approximately 0.2 cc of water (three to four drops) is sufficient to saturate the air within an Amerada RPG-3 Gauge at 160°F, at which temperature the vapor pressure of water is about 5 psia. As the vaporization occurs in a sealed volume, the increase in internal pressure will be in excess of this 5 psi. At higher temperatures the pressures will be higher; however more water will be required to saturate the air within the gauge. Some experimental work was carried out with an Amerada RPG-3 Gauge at 200°F fitted with a 1,000 psi element, both with a dry recording chamber and with a small amount of water added. The results directly proved the existence of the error due to the presence of moisture, and, it is felt, indirectly, due to the differences in sealing temperatures and pressures, as both effects may be ascribed simply to an increase in the moles of gas within the recording chamber. SUMMARY In precision measurements the error introduced by sealing the gauge during a well test at a different temperature and pressure from that of calibration may be corrected for by using the equation presented, or it may be prevented by taking care always to seal the gauge at near calibration conditions. The error introduced by sealing moisture in the gauge may be prevented by taking care to keep moisture out of the gauge, or by removing the moisture by either warming or evacuating the gauge. Both of these errors are independent of the range of pressure measurement and the type of gauge, and are in addition to the usual temperature correction. ACKNOWLEDGMENT Appreciation is expressed to W. B. Kendall, Geophysical Research Corp., Tulsa, Okla., who pointed out the error from differences in sealing temperatures during some winter work in Canada. ***

Jan 1, 1956