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By B. H. Sage, W. N. Lacey, W. M. Morris

The volumetric behavior of isobutane at temperatures below its critical temperature has been studied by several investigators. Seibert and Burrelll measured the vapor pressure of isobutane from the ice point to the critical temperature. Dana and co-workers2 determined among other thermodynamic quantities the density of the saturated liquid and the saturated gas and the vapor pressure from approximately 0 to 130 F. Sage and Lacey3 studied a number of the thermodynamic properties of this hydrocarbon from 70" to 250" F. The specific volume in the gas and liquid region was determined at pressures up to 3000 Ib. per sq. in.? throughout this temperature interval. In addition, the vapor pressures were measured at 30" intervals. These data taken together serve to establish the thermodynamic behavior of isobutane at temperatures between 0" and 250" F. with reasonable accuracy. However, apparently there are no data available at the higher temperatures. For this reason an investigation of the volumetric behavior of isobutane at temperatures between 100" and 460" F. was carried out with apparatus that has been described in another paper (p. 136, this volume). Materials The isobutane used in this investigation was obtained from the Philgas Division of the Phillips Petroleum Co. That company's special analysis upon this sample indicated it to contain less than 0.03 mol per cent of impurities. In order to avoid traces of noncondensable gases, this hydrocarbon material was subjected to two successive fractionations at a high reflux ratio in a column approximately 4 ft. long and % in. in diameter, which was packed with small glass rings. The middle portion of distillate from the first fractionation was used in the second fraction-ation and a portion of the overhead from this second distillation process was repeatedly condensed at liquid-air temperatures at a pressure only slightly above the sublimation pressure of isobutane at this temperature.

Jan 1, 1940

By W. N. Lacey, B. H. Sage, W. M. Morris

The volumetric behavior of isobutane at temperatures below its critical temperature has been studied by several investigators. Seibert and Burrelll measured the vapor pressure of isobutane from the ice point to the critical temperature. Dana and co-workers2 determined among other thermodynamic quantities the density of the saturated liquid and the saturated gas and the vapor pressure from approximately 0 to 130 F. Sage and Lacey3 studied a number of the thermodynamic properties of this hydrocarbon from 70" to 250" F. The specific volume in the gas and liquid region was determined at pressures up to 3000 Ib. per sq. in.? throughout this temperature interval. In addition, the vapor pressures were measured at 30" intervals. These data taken together serve to establish the thermodynamic behavior of isobutane at temperatures between 0" and 250" F. with reasonable accuracy. However, apparently there are no data available at the higher temperatures. For this reason an investigation of the volumetric behavior of isobutane at temperatures between 100" and 460" F. was carried out with apparatus that has been described in another paper (p. 136, this volume). Materials The isobutane used in this investigation was obtained from the Philgas Division of the Phillips Petroleum Co. That company's special analysis upon this sample indicated it to contain less than 0.03 mol per cent of impurities. In order to avoid traces of noncondensable gases, this hydrocarbon material was subjected to two successive fractionations at a high reflux ratio in a column approximately 4 ft. long and % in. in diameter, which was packed with small glass rings. The middle portion of distillate from the first fractionation was used in the second fraction-ation and a portion of the overhead from this second distillation process was repeatedly condensed at liquid-air temperatures at a pressure only slightly above the sublimation pressure of isobutane at this temperature.

Jan 1, 1940

By H. E. Stauss

THE short-time tensile-strength test, while it has not attained the practical importance of the creep test at elevated temperatures, has the advantage of being rapid and is satisfactory for determining relative strengths. For platinum and its alloys, which frequently are used at high temperatures under ill-defined conditions, the short-time test provides useful data that aid in the selection of the most promising alloy for each use. Measurements have been made upon 13 alloys, using wire 0.0031 in. in diameter, the choice of alloys and of wire size being determined by the requirements of a practical problem. Later the measurements were extended to higher temperatures by the use of heavier wire, 0.010 in, in diameter. APPARATUS The use of fine wire made the necessary equipment very simple, since no effort was made to measure the elongation. A small platinum-wound horizontal furnace was used, ½ in. in internal diameter by 1 ft. long, with the wire threaded through it. The wire, clamped at one end while the other ran over a ball-bearing pulley, of a total length of 29 in., was loaded directly by running sea sand into an attached basket, making the rate of loading and not of elongation constant. The sand flowed from a funnel, under a head of 3 in., into the basket. 3 in. below the orifice, at the rate of 170 grants per minute. Pulley friction and bending resist-ance of the wire as well as the force of impact of the sand could be neg-lected, being 3 grams and 0.5 grams, respectively. Furnace temperature .was uniform within ±5° C. over a length of 3 in., although a drift with time occurred, the largest amount being 20° C. No provision was necessary for a controlled atmosphere.

Jan 1, 1939

John J. Porter, Cincinnati, Ohio (communication to the Secretary *):—The remarks of Mr. Firmstone concerning the presence of nickel in Oriskany ores, call to my mind some additional evidence on this point. In 1903, while engaged in the determination of zinc in a number of samples of ore from the Oriskany mine of the Alleghany Ore & Iron Co., I was surprised to discover the presence of nickel and cobalt. As far as I was then able to discover, their present;! had up to this time remained unnoticed. The amounts ranged from 0.05 up to 0.10 per cent. of the combined oxides, and while no attempt was made to separate the metals, the presence of both nickel and cobalt was conclusively proven. Since that time I have learned that traces of these metals are of quite general occurrence in Virginia iron-ores, and more especially in the ores of the Potsdam formation from the western slopes of the Blue Ridge. In certain manganese-ores from this formation, I have found as high as 0.50 per cent. of nickel and cobalt oxides. Any one interested in this subject will find further information in a volume l written by Andrew 8. McCreath, and printed in 1884 for distribution by the Norfolk & Western railway. A number of complete and accurate analyses of Virginia iron-and manganese-ores are given, and practically all show nickel and cobalt in appreciable quantity. Still another source of information on the occurrence of nickel in iron-ores in the United States, for which I am indebted to Charles Catlett, is found in the Tenth Census. Several analyses of Oriskany ores are given: all of which show the presence of nickel, with less cobalt, while the single representative from the Potsdam formation shows nickel, with no cobalt.

Jan 1, 1909

By Walter G. Perkins

In the assay of copper-bearing material for gold and silver, the elimination of copper before the final cupellation is of course essential, because any copper left in the lead-button will carry gold into the cupel; and a method which will effectively remove the copper with the smallest amount of manipullation is desirable. The scorification method is often rendered long and tedious by the necessity of repeatedly re-scorifying the button— to say nothing of the risk of losing Au—Ag thereby incurred. An ore carrying, for instance, 10 per cent,. of copper and only 0.1 or 0.2 oz. gold per ton, cannot be scorified with accurate results, because so many portions would have to be taken in order to get enough gold for weighing. On the other hand, the crucible method, with potassic nitrate and nails, would not do at all in such a case, because all the copper would be reduced by the nails, and (if the charge were 0.5 A. T.) this would defeat cupellation, by causing cupel-absorption of gold. In matte-assays, more concentrated value permits the determination of gold from smaller portions, and thus diminishes the difficulty experienced with ores. The method here described has been severely tested, during use for more than a year, and hart never failed hitherto, in the assay of any ore or product to which it has been applied. It is not proposed as perfect for every variety of ore or matte—probably no method would be that; but it is believed that, intelligently used, with the modifications dictated by practice, it will give better results, with less expenditure of time and labor, than any other known to the writer.

Jan 1, 1902

The following table summarizes the information on the Hurghada field. which is still the major producing field in Egypt. Age of field to end of 1937. years..................... 24 Producing area for gas and oil. acres.................. 1.050 Babbels Total oil production to end of 1937................... 30.188.500 Total oil production during 1936..................... 1.219.406 Total oil production during 1937..................... 1.141.230 Average oil production per acre to end of 1937.......... 28.750 Average oil production per acre-foot to end of 1937.... 2.359 Daily average production (Nov. 1937)................ 3.162 Daily average production per well (Nov. 1937)........ 41.88 MillionB Cu. Ft. Total gas production (Aug. 1925 to end of 1937)....... 4,189 Total gas production during 1936.................... 281 Total gas production during 1937.................... 222.5 Maximum daily average in 1937 (July)............... 0.7 Number of producing wells completed to end of 1937... 97 Number of producing wells completed during 1937..... 3 Number of wells abandoned during 1937.............. 1 Producing wells at end of 1937....................... 78= Total number abandoned wella at end of 1937......... 19 Total number dry wells at end of 1937................ 20 Average depth of bottom of producing horizon, ft...... 1,720 Average depth of top of producing horizon, ft.......... 1,598 Character of oil, approximate average in 1937: gravity at 60" F., 0.900; base, mixed. Character of gas, approximate average during 1937: gallons gasoline per 1,000 cu. ft., 6.9. Producing rock (main): Nubian (?) sandstone. Cretaceous (?); character, sand rock and sandstone. 1 Figures were given in E. tons. A conversion factor of 6.98, based on 0.900 sp. gr., was used to obtain the number of barrels.—Ed. *All pumping.

Jan 1, 1938

By Kandalla Ravindranath, C. C. Patel

Studies of the adsorption of dialkyldithiocarbamates at the surfaces of galena and sphalerite have shown that characteristic contact angles are obtained at galena surfaces in the 7-10 pH range, whereas lower angles are obtained at unactivated sphalerite surfaces even at pH 71 Further, the angles at sphalerite surfaces progressively decrease with increase in pH. However, when sphalerite is activated with cupric sulfate, characteristic contact angles are obtained at pH 7 and beyond. This shows that galena and sphalerite can be selectively floated with dithiocarbamate collectors at pH 7 and beyond. Experimental Materials Ore: The lead-zinc ore for the present study was obtained through the courtesy of the Geological Survey of India from Dariba, Udaipur, Rajasthan, India. The average ore analyzed 15.5% lead, 11.6% zinc, 6.7% iron, 15.6% sulfur and 36.6% acid insolubles. The ore was crushed in a Denver laboratory rod mill and sieved in a Denver automatic sieve shaker to obtain a -200- to +250-mesh (Tyler standard) fraction. This particular size was chosen because it was conducive to good liberation of sulfide minerals, both from one another and from gangue minerals. Collectors: Dimethyl, diethyl, diisopropyl and diisobutyl dithiocarbamates were prepared and purified by the methods described by Klopping and Van der Kerk.2 A freshly prepared 0.03% dithiocarbamate solution in distilled water was used for flotation studies. Frother: A 0.03% solution of pine oil in ethyl alcohol was employed. Activator: 7.3 g of cupric sulfate pentahydrate were dissolved in 1 1 of water and used for the activation of sphalerite. Depressant: 16.0 g of zinc sulfate heptahydrate were dissolved in 1 1 of water and used for the depression of sphalerite.

Jan 1, 1972

By C. Max Bauer

THE most important development in the petroleum industry in Montana, during 1924, was the bringing in of the Hepp well on May 12, by the Midwest Refining Co. This followed three years of active prospecting and drilling in the state by this company. The well is located 35 miles west of Billings, in Stillwater County, and makes a high-grade paraffin oil from the Dakota sand at a. depth of 3825 ft. After flowing for several months at the rate of 150 bbl. per day, the well has been shut in for lack of storage, awaiting further development in the field. TABLE 1. Production Cat Creek and Kevin-Sunburst Fields Month Kevin-Sunburst Pipe- Estimated Cat Creek Pipeline Estimated line Runs Fuel Oil Used Runs Fuel Used January 3,214 0 133,400 140 February 3,250 0 134,248 490 March 11,989 595 163,129 910 April 116,897 1,155 125,918 980 May 179,726 2,310 152,179 770 June 126,131 2,697 122,270 910 July 132,173 2,170 118,034 770 August 202,001 2,695 142,313 1,120 September 187,201 2,135 110,012 350 October 162,589 1,995 121,683 350 November 130,392 2,520 139,900 350 December 107,465 1,780 124,169 0 Total 1,363,028 20,052 1,581,255 .7,140 There are two producing oilfields in the state-the Cat Creek and the Kevin-Sunburst, which produced a total of 2,971,475 bbl. in 1924. The only other field of proved value is Soap Creek, which contains a heavy black oil and is shut in for lack of marketing facilities. Gas is produced for local use at Havre, Chinook, and Baker, and a carbon-black plant is located at Baker.

Jan 3, 1925

By J. D. Mooney, D. L. Darnell

The accompanying chart has been drawn for the convenicncc of engineers as' a means of quickly determining the correct number of plies of conveyor belts operating under specific conditions. The calculations are based on the average safe strength (factor of safety, 15) of the various standard rubber conveyor belts. The calculations assume maximum loading conditions; that is, the belt is considered as carrying the greatest load that it will handle without spillage at ordinary belt speeds. This not only produces the most economical operating conditions, but also the maximum tension in the belt. The chart is a graphical representation of the formula: Where, p = kg W(L + 10H) p = the correct number of plies k = a constant, depending on the type of drive g = the weight 'in pounds per cubic foot of material handled W = the width of the belt in inches L = the length of the belt in feet (approximately twice the center distance). H = the difference in elevation between the head and tail pulleys, in feet. For a simple drive, with a bare pulley, k = ----1 For a simple drive, with a rubber-lagged pulley, k = --- 1 For a, tandem drivej with bare pulleys, k = 1/375.000 For a tandem drive, with rubber-lagged pulleys, k = ---1 The chart is drawn for a simple drive, with a bare pulley (k — =e)1 ; therefore, the number of plies obtained from the chart should be multi- ' plied by the factor 0.83 or 5/6 for simple, lagged drive; the factor 0.67 or 2/3 for tandem, bare; and the factor 0.55 or 11/20, for tandem, lagged. The formula p = kgW(L + 10H) has been developed mathematically

Jan 1, 1916

ARTHUR PHILLIPS,* Bridgeport, Conn. (written discussion?).-It is to, be regretted that the very valuable paper by Messrs. Bassett and Davis did not appear in the early war period. The data presented would have been of inestimable service to inspectors, of cartridge brass who, admittedly, had little or no knowledge regarding the relation of grain size to temperature of anneal, and no real appreciation of, the significance of the Brinell hardness test. The paper is of considerable interest to, metallurgists also. WALTER R. HIBBARD, ? Bridgeport. Conn. (written discussion§).-The writer has carefully studied Messrs. Bassett and Davis's paper with considerable interest, inasmuch as our laboratory has tested cartridge brass by means of a Brinell machine. In March, 1917, at the suggestion of the Technical Department of the American Brass Co., we started a comparison of grain-size measurements and Brinell hardness of-cartridge brass with a gage of 0.1 in. or greater. This was continued until March, 1918, when we adopted the Brinell hardness test as standard for brass 0.1 in. gage or greater, and discontinued grain-size measurements upon this metal. The data collected during the test showed that the Brinell hardness indicated more accurately how the metal acted in actual working operations. It was also more reliable because two manipulators check themselves closer by the Brinell test than by the grain-size measurements. It also consumed less time in making the tests. Alfred V. de Forest, formerly assistant research engineer of our laboratories, has described the apparatus and some of the checking results in a paper read June, 1918, before the American Society for Testing Materials.1 The writer hopes that a more satisfactory. method for testing cartridge brass and gilding in gages thinner than 0.1 in. may be devised than the present method of grain-size measurements.

Jan 3, 1919

By C. H. Pishny, Raymond M. Carr, E. J. Dickinson

Petroleum development in Oklahoma during the year 1932 was rather colorless. The crude price structure, while it was relatively stable, was too low to encourage wildcat drilling and proration restrictions were such that producing wildcats were usually faced with the drab prospect of being limited to 50 bbl. per day. Proration in flush and semiflush areas was for the most part successfully accomplished. Military enforcement of proration rulings was deemed necessary at Oklahoma City. The trend toward cost cutting and abandonment of unprofitable wells continued through the year. It is estimated that 1500 wells were abandoned and it is not unlikely that as many more were shut down which will never produce again. Oklahoma crude oil stocks were reduced by approximately 11 million barrels in 1932. It is generally conceded that inventories of material have been appreciably reduced. Leasing activity was limited principally to rental reductions and to close scrutiny of all lease holdings. There were numerous "leasing plays" based on geophysical information but with few exceptions they were small. It is estimated that over 15 per cent of the acreage under lease at the beginning of 1932 was surrendered during the year. There was a tendency through the year to prospect shallow pay sands formerly passed by in the search for deeper production. This is especially true of the Seminole area, where the Calvin sand received considerable attention, and where some good wells were completed. Prices There were two price changes during the year that affected the majority of crude sales. Using 36 gravity A.P.I. as a basis of comparison, the price was increased on April 11 from $0.77 to $0.92. On Dec. 16, the price dropped to $0.69. During the fall months there were several postings higher than this schedule but all postings were at the same level at the end of the year.

Jan 1, 1933

By R. Raring, W. J. Harris, J. A. Rinebolt

G. W. Geil (National Bureau of Standards, Washington, D. C.)—The authors state that the degree of accuracy realized in the experimental determination of a, is likely rather low. This inaccuracy is attributed to the difficulty in reading the load of the tension machine at the instant of fracture of the test bars. I believe there is another factor which may have added considerably to the inaccuracy in the determination of a,, namely, the determination of 8,. Fracture of a cylindrical tensile specimen of a ductile metal tested in tension at room temperature is generally initiated at the axis and rapidly propagates radially to the periphery of the necked section. During the propagation of the fracture, the metal at the rim of the minimum cross-section extends longitudinally and contracts radially. Thus values of 81, based on diameter measurements made after complete fracture of the specimens do not necessarily represent the strain at the initial fracture." Data obtained at the National Bureau of Standards with a 0.3 pct C steel in the condition as-quenched from 1575°F and tempered at 1000°F for 1 hr and tested in tension at room temperature indicated a considerable "rim effect" and as shown in Fig. 13, resulted in an apparent increase in Sf from 0.90 to 0.98. As the fracture strain of this steel is approximately equal to those of the steels reported by the authors, it seems probable that a similar "rim effect" may have added to the inaccuracies in the reported values of Si and accompanying values of El. R. Raring (authors' reply)—The authors are grateful to Mr. Geil for having called attention to a possible source of uncertainty in the determination of fracture stress, and they are in agreement with the principles upon which his discussion is based.

Jan 1, 1952

By E. C. Burke, W. R. Hibbard

G. B. Craig (University of Toronto, Toronto, O,nt., Canada)—The advent of pyramidal slip at room temperatures in a magnesium crystal (M2,) and the very low value reported for the critical shear stress are puzzling. Table I1 shows the calculated values (approximate) for sin x cos I in this specimen if all the (10l) planes are considered. If So is the shear stress resolved in the direction of glide, on the glide plane, and U, is the stress operative in yield point tests, then: S,, — 325 (0.169) 55gpersqmm (approximately) for 1101: S,, = 325 (0.465) = 151 gpersqmm (approximately) for (0001): S,, — 325 (0.101) - 32.8 gpersqmm (approximately) Thus, we see the pyramidal plane in which the minimum shearing component operated. Barrett"' stated: "Experiments have repeatedly shown that, when there are several crystallographically equivalent slip systems in a crystal, the one having the greatest resolved shear stress will become active. ..." It does not appear to me that the measurements given are conclusive proof that pyramidal slip operated. E. C. Burke and W. R. Hibbard, Jr. (authors' reply) —Although the low value for the critical resolved shear stress for pyramidal slip may be puzzling, there does not appear to be any basis for questioning the validity of the measurements. Under the influence of constraints, slip systems having decidedly lower shearing components may become operative, e.g., "cross-slip" or the "forced glide" in magnesium reported by Bakarian. Since we believe that pyramidal slip occurred in the specimen because basal slip was inhibited, it is not too surprising to find an operative plane with a lower shear stress. -7 C. S. Barrett: Structure of Metals U94jl p. 2J6. New York. McGraw-Hill Book Co.

Jan 1, 1953

By J. M. Vonfeld, V. D. Hanson, W. K. Heinlein

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion No. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and - 3/8-in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3/8-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 1/4 in., and 11/4x3/8 in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into 3/8x0 which is cleaned in the fine coal plant and 3x3/8 for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1952

By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17' of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns'10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

By Jean Howard

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By K. G. Davis

Dilute alloys of silzer in tilz haz been solidzjzed a1 controlled rules, in lzorizontal tubes 2 mrz and 0.5 rn in diam. Radioactive; tracer techniques we?-e used to study solute distvihutions along llze specimens and irmpurity substructures, as functions of the conditions growth. The results have heen mzalyzed using Burton, Prim, and Slichter's tnodel for the solute disty-ihution in the liquid ahead of an advancing solid-liquid interface. DECANTING techniques have been used to establish criteria for the formation of impurity substructure during solidification in several alloy systems An analysis equating the appearance of impurity substructure with the incidence of constitutional supercooling was developed,= in which diffusion was assumed to be the predominant mode of solute mixing in the liquid. Substitution of experimental data into the equations derived from the diffusion analysis gave reasonable values for solute diffusivity in the liquid. However, in these investigations solidification rates of 10 cm per hr and over were used, to minimize the effect of natural conection, whereas for crystals of high perfection lower solidification rates are needed, usually between 1 and 5 cm per hr. A knowledge of the conditions under which impurity substructures will be formed at low growth rates, and the degree of segregation to be expected, is therefore of interest. In the present investigation, radioactive-tracer techniques have been used to study the effect of growth rate, initial solute concentration, and size of specimen on the formation of substructure in uni- directionally solidified rods of dilute silver in tin alloys, over a range of growth rate between 0.5 and 10 cm per hr. Criteria for the formation of substructure were established by auto radiography. This was believed preferable to the decanting technique, for the relationship of the structure on a decanted interface with that of the freezing interface is not clear, since a layer of liquid is left on the surface following decanting.' The effect of substructure on the distribution of solute along the rods was also investigated. EXPERIMENTAL The procedure for sample preparation has been described in detail by einber. Alloys were prepared from tin of 99.999 pct purity and silver of 99.99 pct purity. A"', an emitter of both y and 0 radiation, was used as tracer. Samples of the alloys were drawn up into silica tubes with inside diameters 0.5 or 2 mm, remelted in a horizontal furnace, and solidified at controlled rates. A few centimeters of the samples were left unmelted for a measure of the initial concentration. Total sample length was approximately 20 cm. The temperature gradient in the furnace was kept constant at 36°C per cm in the region corresponding to the melting point for tin. To find how well this corresponded to the actual temperature gradient in the melt, a thermocouple of 38-gage wire was electrically insulated with a thin layer of Sauereisen cement and placed within one of the 2-mm-diam tubes, which was then filled with tin. The maximum diameter of the coated wire was 0.5 mm, the bead of the thermocouple junction being no larger than the diameter of the wire. A plot of temperature vs distance traveled by the furnace is given in Fig. 1 for a rate of furnace travel of 1 cm per hr. The temperature gradient in the liquid

Jan 1, 1967

By A. S. Malicsi, R. J. Lipp, I. Iwasaki

A loch-grade copper-nickel deposit, with an estimated 4.6 Gt (5 billion st) and average analyses of 0.6% copper, 0.2% nickel, occurs in northeastern Minnesota. In addition to copper, nickel, cobalt, and precious metals, the Duluth gabbro contains magnetite, ilmenite, olivine, plagioclase, and biotite. It u estimated that flotation tailings that would be produced by a concentrator of optimal size to sustain a smelter would amount to 20 Mt/a (22 million stpy). The flotation tailings, having already been ground, warrant a closer examination for recovery and use of potential byproducts. Residual sulfide minerals and fibrous minerals may also be isolated and treated separately for useful purposes or for disposal in an environmentally acceptable manner. Two flowsheets were developed; one involving preconcentration by low- and high-intensity magnetic separation and another involving preconcentration by gravity concentration. Concentration methods for recovering and purifying individual byproduct minerals were investigated. From their chemical, physical, and mineralogical characteristics, the potential areas of application and marketabilities of each product fraction were surveyed.

Jan 1, 1985

By N. J. Grant, C. F. Flo, F. B. Cuff

An investigation of the Ti-Cr system has shown the presence of a complete series of solid solutions in the ß phase, with a minimum in the solid us near 50 pct Cr. An intermetallic compound, TiCr2, forms during cooling from the ß solid solution. There is a eutectoid reaction at the low chromium side of the system. IN view of the recognition of the potentialities of titanium and its alloys as important structural materials there has arisen a need for a systematic investigation of various titanium binary diagrams. Of these, the Ti-Cr system was of particular interest because of the improved properties imparted to titanium by small chromium additions. A literature survey disclosed a partial constitution diagram that had been suggested by Vogel and Wenderott,¹ This diagram, shown in Fig. 1, is the result of work done on the Fe-Cr-Ti ternary system. Alloys containing less than 43 pct Cr were not investigated. In addition to this, a study of alloys in the Ti-Cr system was reported by McPherson and Fontana.² Adenstedt3 furnished a number of dilato-meter curves obtained from specimens containing 5, 10, and 15 pct Cr. Very recently, McQuillan4 submitted a proposed diagram covering the complete range of compositions between titanium and chromium. This diagram was in general agreement with the one described here. Experimental Procedure Sponge titanium (99.7 pct) and electrolytic chromium (Bureau of Mines analysis: 99.03 pct Cr, 0.40 pct Fe, 0.53 pct O2) were used for the initial determination of the system. Subsequent refinement of points, particularly for the low chromium side of the diagram, was accomplished by using iodide titanium and high purity chromium (National Research Corp. analysis: 0.050 pct C, 0.045 pct O2). The Ti-Cr alloys were prepared by melting 25 g charges in an enclosed, water-cooled copper crucible using a movable tungsten electrode. The atmosphere was helium, prepurified by first passing it through a drying agent and then through sponge titanium heated to 850°C. Particular care was taken to avoid any large scale segregation resulting from insufficient mixing of the components. Each charge was melted and kept molten for approximately 1 min, allowed to cool, inverted, remelted, and kept molten for an additional minute. In order to ascertain the amount of impurity pickup (oxygen and nitrogen) during the melting procedure, three iodide titanium specimens were melted in sequence and then checked for increased hardness. The specimens in the as-cast condition showed a relatively large hardness increase over the hardness of the as-received iodide titanium. The scattering on these readings was large. However, after the specimens had been homogenized at 840 °C for 2 hr and slowly cooled, the measured increase in hardness over the as-received titanium was small with a corresponding decrease in scatter. The reason for this hardness change is that in heat treating these specimens below the transformation temperature (885°C) there was a conversion from the as-cast structure to the more nearly equilibrium structure of the annealed specimen. The alloys were analyzed for chromium content and although the actual percentage was invariably low the deviation from the nominal composition never exceeded 0.6 pct Cr.

Jan 1, 1953

By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000' and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,' who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7'' became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9'10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal'guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1'-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970