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By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By LIONEL E. BOOTH

ORE tests are made for the purpose of determining the correct methods of treatment for any particular ore. They should be conducted so as to insure that the results obtained in actual mill practice, on ore of similar grade and physical nature, will duplicate the results obtained in the test work. As the expenditure of many thousand of dollars may be involved in the building of the necessary mill, the testing of ores calls for extreme care and skill in handling laboratory machines, and a knowledge of actual practice to guard against the danger of obtaining results in test work that would be impractical to duplicate on a commercial scale. The importance of a correct sample of the ore is at once apparent. No matter with what degree of care the test 4rk is done, it loses its value when made on an unrepresentative sample. It is the first safeguard against future disappointments in the loss of capital and time. A number of failures in the past have been traced directly to faulty or lax methods in obtaining the ore sample.

Jan 1, 1924

By T. M. Allen, W. H. White

THE Greenwood-Grand Forks area of southern central British Columbia, known as the Boundary District, has a long history of mining exploration and production. At the turn of the century this was the premier copper mining camp in the British Empire, its total production amounting to some 20 million tons. Most of this ore came from the great Granby mines at Phoenix, but the Motherlode mine at Deadwood camp, 6 miles to the west, and several mines in Summit camp, 5 miles north of Phoenix, made important contributions. The large deposits were exhausted in 1918 and the district since has seen only desultory exploration and salvage operations. The orebodies are mineralized skarn zones in limestone members of a thick series of Upper Paleozoic sedimentary and volcanic strata. Chalcopyrite is the primary ore-mineral. Copper carbonates and silicates occur sparingly in outcrops, but the oxidized zone generally is very shallow. Much of the surface is mantled by glacial drift which in most places ranges in thickness from 2 to 15 ft. In some of the hanging valleys, however, the glacial drift may be as much as 100 ft thick and may assume drumlin-like forms. In 1951 an ambitious program aimed at the discovery of new orebodies and important extensions of abandoned deposits was launched by Attwood Copper Mines, Ltd. In this district so thoroughly searched by an earlier generation of prospectors, any orebody which had remained undiscovered must have little or no surface indication. Consequently, in addition to the basic detailed geological work, the program of exploration included magnetometer and self-potential surveys. Geological bets and geophysical anomalies were tested further, prior to diamond drilling, by a study of copper distribution in tree twigs and/or in the soil. The soil sampling and analytical methods used and some of the results seem of sufficient importance to warrant this paper. The authors had done some plant sampling in this and other districts, using the dithizone neutral-color-end-point method (Warren and Delavault, 1948, 1949; White, 1950),1-3 but they were unfamiliar with its soil application. Finally, after much experimenting in the field, they adopted the methods described here. These methods are not entirely original or defensible on theoretical grounds, but under field conditions of rapid sampling and analysis the results are reliable enough to be of use. Fig. 1, which shows the results of duplicate analyses of duplicate soil samples taken at 50-ft intervals across an anomalous zone, indicates the relative dependability both of the sampling and analytical methods. Sampling and Analytical Equipment A 2-ft piece of 1-in. solid drill steel, one end sharpened to a broad, conical point. The steel is marked at 1 ft from the point. A 2-ft piece of ½-in. black iron pipe, one end filed to a bevelled cutting edge. The pipe is marked at 1 ft 3 in. from the cutting end. A 3-lb hammer. A plastic or rubberized sheet about 18 in. square. Moisture-proof assay pulp envelopes. A 10-mesh seive made from window screen with the paint burnt off. A small assay spatula. A pan balance sensitive to 10 mg. Two ignition trays about 4 in. square, made of sheet iron turned up along the edges. A Coleman two-burner gasoline stove. An asbestos board about 5x8 in., used as a hot plate on the gasoline stove. A circular aluminum rack to hold 8 test tubes while refluxing (design of Almond and Morris). Pyrex Glassware Large refluxing test tubes, 25x200 mm, marked at 40 ml volume. Breakers, 20 ml. Pipettes, 1, 5, and 10-ml capacity. Graduate, 50 ml. Shaking cylinders, 100 ml, glass stoppers. Burette, 25 or 50-ml capacity, with holder. Chemical Supplies 1 N sulphuric acid. Hydroxylamine hydrochloride, solid crystals. Fisher Alkacid test paper. Copper standard solution. Dithizone standard solution 60 mg per liter. Water reasonably free of metals. Soil Sampling Method: The problem of how to take a soil sample is extremely crucial. The method outlined below, adopted after a number of tests, has the advantages of uniform pattern, uniform depth, and uniform size of sample. The area to be tested was marked off by chain and compass lines 100 ft apart, normal to the strike of possible ore deposits. Numbered stakes were set at 50-ft intervals along these lines and a soil sample was taken at each stake in the following manner. The drill steel was driven into the ground normal to the slope of the surface to the marked depth of 1 ft, moved slightly from side to side, then carefully withdrawn. The iron pipe was inserted to the bottom of this hole, tapped down to the marked depth of 1 ft 3 in. and withdrawn; the 3-in. soil plug in the

Jan 1, 1955

By Webster, Wm. Reuben

THE greatly enlarged demand for small sizes of seamless copper tube which has recently occurred, due particularly to the rapid growth of the electric household-refrigerator industry, has emphasized the superiority of phosphorized to tough pitch copper for the purpose of producing this commodity. In the manufacture of this material exceedingly heavy reductions by cold drawing are employed, customary practice involving as much as 90 per cent. reduction of cross-sectional area in four runs without intermediate annealing. Although this superiority has long been recognized by tube makers, no quantitative expression of it has heretofore been published. It is believed that the data herewith presented mill serve this purpose. Recent investigators are not in agreement as to the relative mechanical properties of copper containing small amounts of oxygen as compared with copper containing sufficient oxygen to produce that condition known as tough pitch. Hanson, Marryat and Ford1 found that "oxygen has a relatively small effect on the properties of copper." Johnson, on the contrary, states "it cannot be denied that it (tough pitch copper) is inferior to deoxidized copper . . . where severe mechanical manipulation is concerned." These authorities in the reports of their investigations, as might be expected from their conclusions, do not present data of a character requisite to a conclusive determination of the question.

Jan 1, 1927

By completing a double-track railroad cut-off, involving a large volume of cut and fill, in addition to a half-mile bridge spanning an important French river, engineers in the zone of the Services of Supply have opened up a route by means of which hours of valuable time are being saved in transporting men and materials to combat areas. Its most valuable feature is that it provides a means for by-passing a certain city where several, French railroad lines converge and where, consequently, congestion of traffic has been responsible for delayed train movements. To avoid a double-track turnout, which would have involved a cross-over cutting one of the French tracks, the two track connections of the cut-off are taken off from opposite sides of the French right-of-way. This involved running one of the new lines of the cut-off out from the main line track on a fill to a point where it could be brought back and over the French track on a steel girder bridge. Beyond this bridge the two tracks of the cut-off converge and straighten out in the standard type of double-track construction. The new cut-off is about 5 3/4 mi. (9 km.) long and has required 160,000 cu. yd. of cut (122,329 cu. m.) and 414,000 cu. yd. (316,527 cu. m.) of fill. In the biggest continuous fill a-yardage of 180,000 has been placed; the road-bed in this section-being-about 40-ft. (12 m.) above the original ground surface. The bridge portion of the cut-off, 2190 ft. (667.5 in.) long, is made up of ninety-nine 14-ft. (4.3 m.) timber spans and sixteen 50-ft. (15.3 m.) steel girder spans. This is the longest bridge which engineers of the American Expeditionary Forces have built in France. The timber spans are supported by pile trestle bents, while the longer steel girders rest on clusters of 43 piles. Two pile drivers of the steam-hammer type worked from each -end of the bridge toward the center of the river, while a drop hammer worked westward from the shore end. In this structure nearly two thousand piles 50 ft. or so in length had to be driven.

Jan 12, 1918

By Guido Bassi

IT is known'" that secondary recrystallization occurs in copper sheet with at least 90 pct reduction after annealing at high temperatures, 700" to 1000°C. Turkalo and Turnbull4 have found recently that secondary recrystallization might occur even after annealing at such low temperatures as 500°C for a high purity, coarse-grained copper sheet. It will be shown in the following that in an electrolytic tough pitch copper wire, with a high degree of deformation, secondary recrystallization might occur at even lower temperatures. A hot-rolled rod of 9.5 mm diam (temperature at which rolling commenced was 850°C) was drawn in continuous drawing machines to 0.4 mm, corresponding to a cross-section reduction of 99.8 pct. The texture in the center of the wire (the sample for X-ray analysis was etched to 0.15 mm diam) is a mixture of the [111] and the [loo] direction, as can be seen from Fig. 1. This is in accordance with the result of Schmid and Wassermann.' After a few minutes annealing of the wire at 200 °C, there is a noticeable recrystallization of the structure with a preferred orientation in the [l00] direction at the expense of the [Ill] deformation texture, as Figs. 2 and 3 show. Farnham and OINeill" reported a similar result. The final recrystallized structure shows mainly the [loo] orientation. There is however a small amount of [111] and random orientations. If the wire is annealed at 400°C, the recrystallized structure first shows a [loo] texture, Fig. 4, but as the annealing time is increased the fine-grained structure transforms into coarse grains, Fig. 5, giving a new preferred orientation, Fig. 6. The calculations show this to correspond to the [I121 direction. Even if the annealing that gives the primary recrystallization is carried out for six weeks at 20O°C, the same secondary recrystallization texture is obtained if the annealing is continued at 400°C. Schmid and Wassermann7 found the [I121 texture, but only after annealing at 1000°C or higher. The appearance of a secondary recrystallized

Jan 1, 1952

By DONALD H. McLAUGHLlN

Few factors have had more influence in maintaining the strength and stability of the United States than our persistent habit of providing .checks and balances to the dynamic powers of free enterprise on the one hand and to the controls and guidance exercised by the State on the other. .Indeed, it is this same concern for matching forces against each other that has given our republic its ability -to preserve a democratic basis of life for its citizens, and yet maintain a ,government that is able to protect the rights of all and to resist and minimize the danger of excessive concentration of authority. Our current efforts to clarify the nation's mineral policies and to define more clearly the role that the governmental agencies should play in conjunction with the functions of private -enterprise again reveal the desirability and advantages of maintaining our traditional controls. At times, the equilibrium has been temporarily disturbed by too great enthusiasm for one or the other of these basic concepts. Sooner or later, however, the balance has been restored by the healthy opposition that is always created by excesses of one sort. At the current stage in our history, the swing toward undue enlargement of the powers of the State seems to have gone dangerously far and we would be untrue 'to our traditional behavior if the group that must demonstrate the virtues of free enterprise did not rally to its support with the utmost earnestness.

Jan 1, 1949

By L. E. Snow, L. F. Pett

AT the Utah Copper Pit of Kennecott Copper Corp. a versatile mobile drill unit has been developed and tested. Through increased drilling speed and additional available drilling time, an improvement of 233 pct in drill performance has been realized. Operators using drill power can quickly and easily convert the unit from a vertical to a toe hole drill. Drilling is done with the machine in line with the unit or at right angles to it. Table I covers the 1950 drill record at the mine, showing the types of machines used and the footage obtained. [ ] Development of the new units was prompted by a desire for solution of the following problems: 1-The ever-expanding operations within the Utah Pit, requiring some 65 miles of transmission pipe lines radiating from a central compressed air plant, have now taxed this compressor plant beyond capacity. While 100 lb per sq in. pressure is maintained at compressors, transmission losses from innumerable small leaks result in low terminal pressure at the drills. Fig. 1 illustrates that while terminal pressure varies according to size of air hose and fittings used, the average drill is operating on air pressures within the 60 to 70-lb range. The compressor plant is operated primarily for air rock drills. All drilling is done on day shift, but it is necessary to run two of the three 3720 cu ft capacity compressors during night shift in order to prevent drastic loss of pressure through leaks. On day shift all three compressor units are operated at capacity, so that there is no reserve safeguard available for extensive repairs to any compressor. The calculated volume of compressed air required for operation of 25 drills is but 33 pet of three day-shift compressors. While compressed air is being used to a minor extent for purposes other than drilling, it is felt that satisfactory substitute facilities could be provided in the event that air lines were no longer available. 2-Drill performance has increased beyond the capacity of present 3 ½ -in. drifter machines. 3-The installation, maintenance, and moving of air lines in routine mining is a growing problem. The 2-in. level lines are placed outside electrification towers and must be moved to new location upon completion of each shovel cut. In addition to these moves it is often necessary to dismantle level lines so that excessive shovel spillage, or material covering track following a blast, can be pushed in the clear with bulldozers. Where level room is limited, it is often necessary to remove air lines in giving bulldozers room to prepare grades for wagon drills. In spite of precautions taken, many level lines become buried, twisted, and constricted, with excessive air loss resulting. Excessive back break in blasting often leaves several sections of air line suspended in mid-air. Occasionally air lines come in contact with defective electric transmission towers, so that holes are burned through pipe. 4-Rail-handling of drilling equipment such as wagon drills from one location to another requires considerable locomotive crane crew time. Any new unit developed should travel under its own power. 5-Present practice requires accessory material including hose, water pressure tanks, water barrels, drill steel, and bits to be transported by means of push cars when drill locations are changed on any level. 6-In order to supply numerous drill locations with material, many stock piles of new drill rods, drill bits, and other essentials must be left at strategic points, usually in the vicinity of powder magazines. This practice makes for poor housekeeping and contributes to the loss of supplies. Planning the Unit It was felt that a mobile drill unit which would rectify the foregoing problems should meet certain demands: 1-It must furnish compressed air to operate a 4-in. rock drill at a pressure of 90 to 100 lb.

Jan 1, 1952

By D. Kramer

HASEN1 has published a phase diagram for the zirconium-nickel system. This phase diagram has been redetermined by Hayes, Roberson, and paasche2 in the range 0 to 50 at. pct Ni. Recently, Smith and Guard3 have published a tentative diagram for the

Jan 1, 1960

By W. D. BRENNAN

FOR a considerable number of years past, there has been a shortage of experienced coal miners at the coal mine of the Phelps-Dodge Corp. This is probably due, to some extent, to the mines being so far south of the main western coal producing regions, so that experienced men secure employment before reaching this point. These mines are at Dawson, New Mexico, which is in Colfax County, near the Colorado line. The district is known as the Raton field, and the seam being worked is known as the Raton or Blossburg seam. The mines operated are Nos. 1 to 6, 8 and 9. The daily out- put at the present time, with restricted operations, is about 4000 tons, but the daily capacity is about 5500 tons. The mines are so grouped that the coal is dumped over four tipples. The mines are about twenty-five years old and extend as much as three miles under ground; they are all drift openings, with trolley, storage battery, and mule haulage. At the same time that the shortage of miners existed there was a surplus of common labor seeking employment. We learned that the Copper Queen. Branch of Phelps Dodge Corp. conducted a training school in one of its mines which had worked out very satisfactorily, and thus gained the idea of attempting such a school in the coal mines at Dawson.

Jan 1, 1929

By E. V. Potter, E. T. Hayes, H. C. Lukens

Large volumes of hydrogen are liberated at the cathode during electrolytic precipitation of manganese. Most of the gas escapes from the electrolyte, but a considerable amount may be entrapped in the manganese plate. Gas has been observed to escape from manganese melts in puffs that bite at the surface. It has been reported that castings made with electrolytic manganese tend to rise in the molds; for this reason the manganese is often treated to remove hydrogen before the melt is made or it is premelted and used as cast manganese in making the alloys. The effect of hydrogen on the properties of manganese and its alloys is not known, but its effect on iron and iron alloys has been studied extensively.l.2 The close relationship between iron and manganese suggests that hydrogen may have a similar effect on the properties of manganese and its alloys. The purpose of this investigation was to determine the amount of hydrogen or other gases in typical commercial electrolytic manganese sheet and to investigate ways of removing it most conveniently. Apparatus The apparatus used is shown schematically in Fig. I. It consists of a chamber A in which the metal sample is placed, a vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The specimen chamber was made of two concentric quartz tubes. The outer one, a, connects with the closed gas system and is surrounded by the furnace G. A second tube, b, fits closely inside a and has a small end that projects into the space for the specimen and holds the thermocouple for measuring the temperature of the sample. The inner tube is joined to the outer tube outside the furnace, with rubber tape and sealing wax, to prevent gas leakage into or out of the closed system. This type of specimen container is loaded very easily and can be used several times if molten metal does not come in contact with the quartz. An ordinary mercury manometer B is used to measure the pressure in the system. The volume gauge C is essentially another mercury manometer, but the volume of the column is much larger than normal and the height of the mercury can be varied by raising or lowering the well H. In this apparatus the tube had a volume of IOO C.C. for a 60-cm. length. For larger changes in gas volumes, auxiliary containers F were used to increase the volume of the system by known amounts. Valves were arranged so that these auxiliary containers could be filled from the system and evacuated by the pump as often as necessary to accommodate the increases in the volume of gas in the system. The furnace G, used to heat the samples, was equipped with an automatic temperature controller, which maintained the desired temperatures within ± 5°C.

Jan 1, 1945

By C. G. Dunn

With respect to theories of recrystalliza-tion in metals plastically deformed. it has been said that the present status of this subject is far from satisfactory.1 It may also be said that before any mechanism of recrystallization for metals and alloys can be set forth in a satisfactory manner, there must be made available considerable data on orientation changes that occur during the deformation and recrystallization processes. Although extensive data have been published on recrystallization in single crystals and in poly-crystalline specimens, more results of a type that can be classified according to simple orientation changes would be desirable in this complex field. It might even be said that before classifications are made according to types of orientation changes, it may be possible to classify a considerable amount of data into certain kinds of orientation states if groups of common or nearly common orientation occur. Methods for computing the probability of occurrence for various types of groups have been published2 and it has been pointed out in particular that it should be possible to analyze orientation data for high-order twin relationships between old and new grains even when agreement is not at all exact. In this connection, work on recrystallization in silicon ferrite reported in a paper concerned with complex groups of annealing twins3 indicated that some data were consistent with primary nucleation OCcurring according to a second-order or a third-order twin transformation. However, further work in this latter direction was definitely needed. It is, therefore, the purpose of the present paper to report data and analyses for primary nucleation in silicon ferrite following small deformations that have been carried Out at the Pittsfield Works' Laboratory of the General Electric Co. Analyses have been made with the aid of standard groups of twins that are reported elsewhere.4 PReparation oF Specimens and Experimental Procedure The material used in the present investigation was taken from the same heat of steel as that .used in a prior report.3 The finished strip in both cases was made by the Allegheny-Ludlum Steel Corporation according to methods that produce a high degree of preferred crystal orientation. Samples with large grains had the following composition: 3.45 per cent Si, 0.003 C, 0.008 P, 0.020 S, 0,075 Mn, 0.03I A1 and 0.072 Cu. Thickness of specimens was 0.012 inches. Plastic deformation was produced by cold-rolling the samples on a mill with 8-in. diameter rolls, the plane of the sample in each case coinciding with an XY plane (the plane of projection for the stereo-graphic plots) and the elongation occurring in the X direction. In general, elongations were held to about 3 or 4 per cent.

Jan 1, 1945

By E. C. Nelson

An equation is derived for calculating approximately the solubility of nitrogen in an alloy steel over a temperature range from 1200" to 1900°C using data on the effects of alloys on the activity coefficient of nitrogen in iron at 1600°C. Calculated values are compared with experimental data. STUDIES involving the solubility of nitrogen in complex iron alloys have been aided by a system devised by Lanenberg for calculating the solubility of nitrogen in ternary and higher alloys of iron at 1600C using available data on the activity coefficient of nitrogen in binary alloys. Calculated nitrogen solubilities agree well with experimental determinations on complex alloys,' and the calculation procedure is useful when experimental data on specific alloys are not required. A method for extending calculations of nitrogen solubilities in alloy steels to temperatures other than 1600°C would be useful because of the paucity of experimental data in this area. Assumptions which must be made to permit this calculation introduce an element of approximation; however, the calculation is useful in cases where a large number of alloys and temperatures are under consideration, and the precision of experimental measurements is not required. The activity coefficient can be freed from the isothermal restriction of Langenberg's calculation if it is assumed that the solution is "regular". This is a reasonably good assumption for solutions of nitrogen in iron alloys, because usually they are dilute and the heat of solution is relatively small. The presence of large amounts of certain alloying elements would make this assumption less tenable.3 One of the properties of a regular solution is: when "f" is the activity coefficient of a solute and "T" is the temperature in OK. If the activity coefficients at temperatures T and T2 are denoted by subscripts 1 and 2 respectively: The activity coefficient of nitrogen in a complex alloy then can be calculated at any temperature from the sum of the effects of the other solutes on the activity coefficient of nitrogen at 1600°C. It will be convenient to incorporate this expression into an equation which will give directly the logarithm of the solubility of nitrogen at any temperature in the presence of alloys. Two constants, the solubility of nitrogen in pure iron at 1600 "C and the partial molar heat of solution of nitrogen in iron are required. The heat of solution value of 1400 cal at 1600 °C quoted by Kubaschewski and vans will be used. The accuracy of the calculation will suffer if the heat of solution should change materially with temperature. In the absence of experimental data on the temperature dependence of this quantity, it will be expedient to restrict the application of the calcula-

Jan 1, 1963

By William Brewster

DATING back some five years ago, various foundries made inquiries as to the probable total carbon content in a given specification and grade of pig iron. Up to that time we had no data, and except for a few occasional determinations of total carbon, no attempt had ever been made to set up routine determinations of total carbon. In fact, at that time, a cast analysis was considered sufficient, without examining at further length into possible variations of analysis between ladles of the same cast. In view of the various inquiries as to total carbon, we sampled all piles of all grades of pig iron, making complete analyses. Finding some variation in carbon content, we secured more samples and plotted the carbon content with respect to silicon in each grade of iron except for the higher phosphorus foundry iron, where it was necessary to divide the group into twenty-point phosphorus ranges. This is easily understood, owing to the falling off of carbon content with the increase in phosphorus con-tent, silicon in each case being the same. In addition, these curves clearly demonstrate the lowering of the carbon content as the silicon is increased. In order to insure accuracy and reliable determinations the following method of sampling and analysis was employed: Two pigs selected from each end of the car, each car containing iron from one 50-ton ladle, are drilled with a 5/16-in. drill all the way through from top to bottom in the center of one section of the pig. The drillings are collected and transferred to an 80-mesh sieve; the portion passing through and the portion retained are placed in separate envelopes and labeled accordingly. The amount of sample in each envelope is weighed to obtain the proportionate amount of coarse and fine drillings, then a factor weight of sample (1.3636 grams) made up of proportionate

Jan 1, 1936

By Lyndon L. Foley

The proper spacing of oil wells is a problem of vital importance to the oil industry. Conservation demands a maximum recovery, while economic considerations attach primary importance to profitable extraction of oil. Formulas have been evolved,1-4 which attempt to solve the spacing problem mathematically, using reservoir characteristics as factors. Comparisons have been made of fields producing from supposedly similar sands, which have been drilled to varying densitiesl5,6 and also of different leases in the same field. 5-8 Intermediate wells have been drilled in old, depleted fields to test the efficiency of drainage by the original operation.9-11 Intermediate wells have been drilled also to obtain cores of the depleted sand for analysis, from which to learn the degree of efficiency of extraction. The problem is being attacked by many students, and along several different lines. Unfortunately, the fields now depleted were produced generally without restriction, and conclusions drawn from them may not apply to fields operated under restricted production. Reservoir conditions in a restricted field, especially reservoir pressures and pressure gradients within the reservoir, are quite different from those in a field produced to capacity. Many people have held the idea that the closer the spacing, the greater the recovery. This general statement is not always true, as other factors than well spacing enter into the recovery problem. Cutler,5 who has been quoted frequently by advocates of close spacing, limited his conclusions to gas-drive fields, and to the particular fields and spac-ings that he investigated. Hill and Sutton7 analyzed four tracts in the Powell field; the tract most closely drilled had the third largest recovery per acre-foot, and the tract with the widest spacing had the second largest recovery per acre-foot. A search of the references to well spacing in the publications of the U. S. Bureau of Mines5,13-19 discloses repeated condemnations of the wastefulness of the practice of town-lot drilling.

Jan 1, 1938

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By O. F. Thornton, D. L. Marshall

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By D. L. Marshall, O. F. Thornton

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943