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By H. W. Knott, M. H. Mueller

The crystal structures of Ti2Cu, Ti2Ni, Ti4Ni2O, and Ti4Cu20 have been determined using powder specimens examined by X-ray and neutron diffraction. Lattice constants have been determined for all four phases using X-ray powder diffraction films. Atom positional parameters of all four phases have been determined from observed neutron intensities. X-ray diffraction calculated intensity data have been presented also for the phase Ti2Cu to point out the particular suitability of neutron diffraction in this case. Interatomic distances have been determined using the positional parameters obtained from neutron diffraction. ALTHOUGH some investigations of the crystal structures have been made of these four compounds previously,'-13 it was the purpose of the present investigation to expand the previous work in order to locate the various atoms, determine their coordinates, and to confirm or to correct some of the previous work. It was convenient to group these four compounds together since they are related chemicallv and/or structurally. The compound Ti2Cu is tetragonil; and Ti2Ni, Ti4Ni2O, and Ti4CU2O are all large fees of the same space group. Ti2Cu has been previously reported as a fee phase by Laves and Wallbaum;1 and Rostoker2 which was possibly the oxide phase, Ti4Cu20. Joukainen, Grant, and Floe;3 and Trzebiatowski, Berak, and Ramotow-ski4 have also reported a phase of this composition. karlsson5 has reported a small fct phase of the composition Ti3Cu which may be the presently discussed Ti2Cu phase. More recently Ence and Margolin6 have reported a small fct phase for Ti2Cu and the present authors7 together with Nevitt8 have briefly reported it to be a bet related to the fct with a co three times the length of the co of the fct and have also reported that this phase has a very limited composition. Further refinements will be reported which have varied some of the parameters of this bct structure slightly. Ti2Ni has been reported as a fee phase by Laves and wallbaum;1 Duwez and taylor;9 Rostoker;2 Poole and Hume-Rothery;10 and Yurko, Barton, and parr.11 In a later paper Yurko, Barton, and parr12 have given the complete structure of this phase based on an X-ray diffraction study which was independently confirmed with neutron diffraction by Mueller and knott.7 Additional crystal structure information will be given. Ti4Ti2O, Ti4Cu2O, and a number of other compounds including Ti4Fe2O have been reported as fcc phases by Rostoker,2 and more recently Nevitt13 has confirmed the Ti4Ti2O phase. Rostoker,2 however has reported diffraction lines for Ti4Fe2O which do not have all odd or all even indices. These lines, therefore, cannot be observed if this compound has a fee structure. This same error has crept into the diffraction results reported for TiNi2O and Ti4Cu20 in the ASTM powder data which has been credited from Rostoker's data. Complete crystal structures of these two phases will be presented. Although all four of these structures have large unit cells and hence do not lend themselves for completely resolved neutron powder patterns, a sufficient number of individual reflections was observed for solving the structure. They also serve as good examples of some of the advantages to be gained by using both neutron and X-ray diffraction techniques. EXPERIMENTAL PROCEDURE All of the alloys were prepared by arc melting. The starting metals had the following purity: Cu 99.999 pct, Ni 99.83 pct, and Ti 99.92 pct. Oxygen was introduced into the two oxide phases as chemically pure TiO2, with the remainder of the titanium coming from the above mentioned metal. All of the sample buttons were annealed in evacuated Vycor tubes, the two binary phases for 5 days at 700°C and the two oxide phases for 3 days at 900°C. Oxygen analyses were performed on all four phases by two independent laboratories with the following amounts of oxygen present in atomic percent; Ti2Cu-0.06, Ti2Ni-1.03, Ti4Ni2O-13.95, and Ti4Cu20-13.87. The stoichiometric amount for the oxide phases is 14.29 at. pct. Since all of the samples were very brittle they were easily reduced to a powder for diffraction measurements. The lattice constants given in Table I were determined for the four compounds from X-ray diffraction patterns of powder samples exposed to filtered copper radiation using a 114.59 mm diam Debye-Scherrer type camera using the Straumanis loading. None of the patterns showed a detectable amount of a second phase. The lattice constants were obtained from an IBM 704 computer program employing a least squares treatment with systematic correction terms as previously reported.14

Jan 1, 1963

By Jay Carpenter

THIS paper deals with only one step in the treatment of ore at the West End mill; not because the other steps are repetitions of practice in other mills, but because in this particular step there is in use the Trent agitator. This device, although it has apparently failed in many mills, is here giving excellent service and has proved to be well adapted for making a thorough replacement of pregnant solution with a minimum amount of barren solution. The strong and weak points of this agitator, its present simple construction, and its use as a thickener for agitator or battery pulp are features of interest; but perhaps the point of greatest interest to the metallurgist in this day of continuous decantation is its use in a series of tanks for slime treatment by the replacement method. The agitating department of the West End mill consists of six redwood tanks, 24 ft. in diameter, 18 ft. high, each equipped with aTrent agitator, a centrifugal pump, and a motor. The pulp is transferred by a pump from the top of a flat-bottomed tank to a set of arms and nozzles in the bottom of the tank, at just sufficient pressure to cause the arms to revolve. The streams from the many nozzles keep the bottom of the tank clean, and these streams, coupled with the effect of the revolving mechanism and the ascending current, keep the pulp in constant motion and of constant gravity. .These agitating tanks hold 90 tons of dry slime and 202 tons of solution with a 1.24 pulp, our ore having a specific gravity of 2.7. This capacity is about 10 per cent. in excess of the standard 15 by 45 ft. Pachuca tank. The tanks are connected in one series for continuous agitation, the pulp for each agitator being drawn by its pump through a branch suction from near the top of the preceding tank and. delivered to the bottom of the tank by the agitator arms along with the regular pulp of that agitator. This method works automatically, since the flow through the branch suction varies directly with the difference in head of the two tanks. The chance for new pulp to pass out quickly is, therefore, much less than in many other systems of continuous agitation, since the new

Jan 8, 1915

By Jay A. Carpenter

This paper deals with only one step in the treatment of ore at the West End mill; not because the other steps are repetitions of practice in other mills, but because in this particular step there is in use the Trent agitator: This device, although it has apparently failed in many mills, is here giving excellent service and has proved to be well adapted for making a thorough replacement of pregnant solution with a minimum amount of barren solution. The strong and weak points of this agitator, its present simple construction, and its use as a thickener for agitator or battery pulp are features of interest; but perhaps the point of greatest interest to the metallurgist in this day of continuous decantation is its use in a series of tanks for slime treatment by the replacement method. The agitating department of the West End mill consists of six redwood tanks, 24 ft. in diameter, 18 ft. high, each equipped with a Trent agitator, a centrifugal pump, and a motor. The pulp is transferred by a pump from the top of a flat-bottomed tank to a set of arms and nozzles in the bottom of the tank, at just sufficient pressure to cause the arms to revolve. The streams from the many nozzles keep the bottom of the tank clean, and these streams, coupled with the effect of the revolving mechanism and the ascending current, keep the pulp in constant motion and of constant gravity. These agitating tanks hold 90 tons of dry slime and 202 tons of solution with a 1.24 pulp, our ore having a specific gravity of 2.7. This capacity is about 10 per cent. in excess of the standard 15 by 45 ft. Pachuca tank. The tanks are connected in one series for continuous agitation, the pulp for each agitator being drawn by its pump through a branch suction from near the top of the preceding tank and delivered to the bottom of the tank by the agitator arms along with the regular pulp of that agitator. This method works automatically, since the flow through the branch suction varies directly with the difference in head of the two tanks. The chance for new pulp to pass out quickly is, therefore, much less than in many other systems of continuous agitation, since the new

Jan 1, 1916

By Francis B. Foley

In examining steel under the microscope, one is constantly confronted with structures that are difficult to interpret. Recently, in a collection of samples for exhibition purposes, the writer found a piece of open-hearth runner metal, 2 in. (50 mm.) in diameter, that had been fractured for use as a sample of cast-steel structure. On polishing and etching a section for the purpose of photographing a field to typify the microstructure of steel in the "as cast" condition, a variety of structures was found (Fig. 1) so arranged as to arouse interest at once. For a distance of about 0.065 in. (1.6 mm.) from the skin of the runner, normal ingot structure was found (Fig. 2); this was followed by a zone, about 0.215 in. (5.5 mm.) wide, of considerably lower carbon content in which occurred a most pronounced Widmannstattian structure (Fig. 3); from this point on to the center of the runner, the metal was again of normal ingot structure (Fig. 4). Representative samples taken from the metal in the three zones showed the following analysis: Carbon Nickel Chromium Per Cent. Per Cent. PeR Cent. Metal from skin........................... 0.34 1.26 0.63 Widmannstattian zone.................... 0.21 1.18 0.63 Metal from center......................... 0.34 1.32 0.67 Such a condition might result from decarburization followed by recarburization of the skin. This section came from one of the branch runners to the bottom of the mold, not from the main runner, and it is difficult to conceive of decarburization occurring in this portion of a runner. If the metal were stripped while quite hot, some oxidation would take place but the recarburization is unaccounted for. It could not occur by segregation after solidification—the tendency then is for diffusion and homogeneity. The following seems to fit the conditions and is offered as an explanation. The outside layer of normal structure 0.065 in. (1.6 mm.) thick was chilled on the walls of the runner brick when the molten metal first entered the runner. As the molten metal flows by, the outside of the stream

Jan 1, 1920

By R. M. Brick, Arthur Phillips

The Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic problems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segregation. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute concentration, with a resultant normal segregation or coring effect during freezing. Theoretically, musion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions aluminum-copper alloys segregate inversely and aluminum-magnesium alloys segregate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By W. N. Page

The Red-Ash colliery was the scene, March 6, 1900, of an explosion by which some fifty men were killed or wounded, and much property was injured or destroyed. On March 19th, the earliest date at which entrance was practicable, I examined the mine with the view of determining the extent, cause and point of origin of the explosion, and with the permission of Mr. F. Howald, the manager, and the owners of the property, for whom the examination was made, I present in this paper some results of that examination, comprising the essential portions of my report to them. Location and Plan of the Mine. The Red-Ash colliery, situated on the south side of New river, next below the Rush Run mine, with which the underground workings are connected, is a drift-mine, the entrance to which is on a slope, about 500 ft. above the river. (Fig. 1 is a plan of the workings, in which the points where human bodies were found are designated by numbers.)

Jan 1, 1901

By K. C. Sclater

GAS as a factor in the efficiency of oil production, might be a better title for this paper as it deals in general with the significance of the gas-oil ratio as an index of the efficiency of oil production and briefly discusses oil production methods with reference to the gas-oil ratio in wells, particularly during the early life of a field. In the recent hearings held at Washington before the Federal Oil Conservation Board the fuller utilization of the energy contained in the gas occluded in or associated with the oil underground was stressed by some of the speakers when referring to greater ultimate recovery of oil. One speaker commenting on this point said in part, "There is ample evidence indicative that if the gas associated with the petroleum in our fields were conserved and elevated gas pressure maintained in the oil sands during their productive life, the ultimate production of oil could be greatly increased."

Jan 1, 1926

By William Mikulas

LITTLE work has been done in the field of the nickel-tin binary system. The complete diagram has been investigated on two occasions, but the results are in very poor agreement. The structure of a compound NiSn, and the solubility of tin in nickel have been determined by X-ray methods. Several investigations have been made of the liquidus curve, and the compositions of the eutectics have been determined. A study of the literature, however, shows that there is no satisfactory agreement between the data presented in the various papers. The present investigation was undertaken in an attempt to determine the equilibrium conditions, and to correlate X-ray with metallographic data. The equilibrium diagram was determined by thermal and metallo-graphic means, and the solubility of tin in nickel further investigated with X-rays. Powder diagrams were made of the intermetallic com-pounds, and three of the structures were partly determined. No attempt was made to determine the range of homogeneity of the inter-metallic compounds.

Jan 1, 1937

By Eugene Holman

UINQUESTIONABLY the petroleum industry not only can supply the world's present oil requirements but even can meet a considerable increase in demand if it should come. The United States produced last year 1 1/3 billion barrels of crude oil, or more than 60 per cent of the world's total. It could have provided more, if needed, because we has a large shut-in crude producing capacity. Our refining capacity of 4,500,000 0 barrels per day is more than 2 per cent above our average refinery run for 1940. Adequate crude supplies and manufacturing facilities also exist outside of the United States. Large crude reserves exist in South America, in Iran and Iraq, in Russia and Romania, in Sumatra and adjacent islands. The refineries of the Dutch West Indies, of Iran, and of the Netherland East Indies are well located in relation to crude reserves and world trade lanes. Furthermore, flexibility in the manufacturing facilities permits adjustment of yields to meet a considerable range in variations between demands for products. Only with regard to 100-octane aviation gasoline is there any apparent refinery problem. Even here so far as this country is concerned, additional refining facilities can be installed well within the time that would be required to turn out the airplane engines which will use this super fuel.

Jan 1, 1941

By E. Gybbon Spilsbury

(Pittsburg meeting, March, 1910.) THE recovery of gold and silver from their ores by means of the cyanide process has been so successful in the last few years that any radical improvement would seem impossible; yet the appliance to which I wish to call attention in this paper is really a radical departure from the methods now in general use. The most modern and approved of these, known as the all-sliming method, depends for its success on the grinding of the. ore so fine that practically 90 per cent. of it will pass through a 200-mesh screen. The slimes thus produced are then agitated and aerated in tanks of various types. The main object of this treatment is to insure such a thorough admixture of the pulp and solution that every particle of the ore is surrounded by a volume of solution sufficient to insure the dissolving of the whole of the gold- and silver-content. In addition, in order to expedite the action of the cyanide, and to oxidize such elements as would, if left in their active state, become cyanicides, air is blown in under pressure. In the Pachuca tank, this air is the active and sole means of agitation. The chief objections to all the methods off agitation used heretofore are the expense of operating and maintaining the mechanical devices for keeping the pulp in suspension, and the length of time required to obtain a fairly complete extraction. of the values. These objections are inherent to any method of agitation effecting a circulation of the pulp and the solution together, by giving the whole mass a circular movement, as in the low-tank system, or a vertical circulation, as in the Pachuca-tank system. In both methods, the particles of ore are kept traveling in the same direction as the solution, and with very little difference of speed; so that, while the whole mass is in

May 1, 1910

Trans. No. Place Date Vol. Page 1. Wilkes-Barre Pa......May.71 1 3 2. Bethlehem, Pa.........Aug., '71 I 10 3. Troy, N.Y............Nov..: 71 1 13 4. Philadelphia, Pa........Feb., 72.. 1 17 5. New York. N. Y.*......May, '72.. 1 20 6. Pittsburgh. Pa.........Oct..' 72.. 1 25 7. Boston, Mesa..........Feb., '73.. 1 28 8. Philadelhia, Pa.*......May, '73.. 2 3 9. Easton, is............Oct..' 73.. 2 7 10. New York, N. Y.......Feb..' 74 . . 2 11 11. St. Louie. Mo.*........May,' 74 . . 3 3 12. Hazleton, Pa...........Oct., '74.. 3 8 13. New Haven Conn......Feb., '75.. 3 15 14. Dover,N.J.*..........May, 75.. 4 3 15. Cleveland,O...........Oct. 75. 4 0 16. Washington D. C......Feb.'' 76.: 4 18 17. philadelphia, Pa.......June,: 76.. 5 3 18. Philadelphia Pa........Oct 76.. 5 19 19. New York, N. Y.......Feb: '77.. 5 27 20. Wilkes-Barre. Pa.*.....Mag :77.. 0 3 21. Amenia N. Y..........Oct. 77.. 6 10 22. Philadeiphia Pa........Feb.;' 78. . 6 18 23. Chattanooga' Term.*. . . May' 78. . 7 3 24. Lake George: N. Y....: Oct. 78. . 7 103 25. Baltimore, Md.*.......Feb:' 79.. 7 217 26. ~ittsburgi, Pa.........~a;' 79.. 6 3 27. Montreal, Canada......~ept.;' 79.. 8 121 28. New York, N. Y.*......Feb., '80.. 8 275 29. Lake Superior, Mich....Aug., '80. . 9 1 30. Philadelphia, Pa.*......Feb., '81. 9 275 31. Staunton, Va..........May, '81. .10 1 32. Harrisburg, Pa.........Oct.. '81..10 119 33. Washington, I). C.*....Feb., '82. . 10 226 34. Denver. Colo..........Aug.. '82. . ll 1 35. Boston. Mass.*.........Feb.. '83..11 217 38. Roanoke, Va...........June, '83.. 12 3 37. Troy, N. Y...........Oct.. '83. .12 175 38. Cincinnati. O.*.... Feb, '84..12 4 39. Chicago Ill............May, '84. . 13 1 40. philadelphia, Pa........Sept., '84. . 13 285 41. New York, N. Y.*......Feb., '85. . 13 586 42. Chattanooga, Tenn.....May, '85..14 1 43. Halifax, N. S..........Sept., '85.. 14 307 44. Pittsburgh, Pa.*........Feb.. '86 . . 14 587 45. Bethlehem. Pa.........May, '86 .. 15 Ixiii. 46. St. Louis, Mo..........Oct, 86.. 15 Ixx. 47. Scranton, Pa.*.........Feb.', '87. . 15 lxxvi 48. Utah and Montana.....July '87.. 16 xvii. 49. Duluth, Minn...........July' '87. -16 xxiv. 50. Boston. Mass.*.........Feb.: '88. . 16 xxviii. 51. Birmingham, Ala.......May, '88. .17 xix. 52. Buffalo N. Y..........Oct. '88.. 17 xxiv. 53. New york, N.Y........feb.' ;89 . . 17 xxxi. 54. Colorado..............June' 89 . . 18 xvii. 55. Ottawa, Canada........Oct., 89. . 18 xxiv. 56. Washington, I). C.*. . . Feb. 90. .18 xxx. 57. New York, N. Y........sept:, '93. .19 vii. 58. New York, N. Y.*......Feb. '91. . 19 xxv. 59. Cleveland, O.......... June, :91 . .a xvi. 60. Glen Summit, Pa.......Oct, 111. . 20 lxi. 61. Baltimore, Md.*.......Feb.: '92. .21 xix. 62. Plattsburg, N. Y.......June, '02. . 21 xxxiii. 03. Reading. Pa...........Oct., :92. .21 xliv. 64. Montreal. Canada*.....Feb. 93..21 65. Chicago, Ill............aug.: '93..22 XI. 66. Virginia Reach. Va.*. ...Feb., '04. .24 xwl. 67. Bridgeport Coon.......Oct., '94..24 xxx?. 08. Florida ...'............Mar., '95. .25 xix 69 Atlanta. Ga......... Oct 95. 25 xi 70. Pittsburgh. Pa.*........Feb., '96.. 26 xvii. Trans. No. Place Date Vol. Page 71. Colorado..............Sept. '96. .26 xxix. 72. Chicago, Ill............Feb.. "97.. 27 xvii. 73. Lake Superior..........July '97. .27 xxx. 74. Atlantic City, N. J.*. ..Feb.: :98. .28 xvii. 75. Buffalo N. Y..........Oct. 08. .28 XXXVI. 76. New York,N. Y.*......Feb.: '99. .29 xvii. 77. California.............Sept., ;99. . 29 xlix. 78. Washington, D. C.*.....Feb., 00. .30 xix. 79. Canada...............Aug.. '00. .30 xlv. 80. Richmond. Va.*........Feb.. '01. . 31 xix. 81. Mexico................Nov..'01.. 32 cxviii. 82. Philadelphia Pa. $......May, :02. . 33 xxxv. 83. New Haven, Conn......Oct.. 02.. 33 xlvii. 84. Albany N. Y.*........Feb '03. .34 xxiii. 85. New York, N. Y........Oct.': '03. .34 xi. 86. Atlantic City. N. J.*....Feb., '04. .35 XXIII. 87. Lake Superior..........Sept.'04. .35 dii. 88. Washington. D. C......May' '05. .36 xlii. 89. British Columbia.......July, '05. . 36 90. Bethlehem. Pa.........Feb. '06. .37 xli. 91. London, England.......July: '06. .37 xlviii. 92. New York, N. Y........April, '07. . 38 lii. 93. Toronto, Canada.......July. '07. .38 lix. 94. New York, N. Y........Feb., :08. .39 xli. 95. Chattanooga, Tenn.....Oct.. 08..39 xlviii. 06. New Haven Conn......Feb. '09. .40 xli. 97. Spokane,Wash.........Sept:.'09. .40 xlviii. 98. Pittsburgh, Pa.........Mar.,'10. .41 xxxviii. 99. Canal Zone............Nov.,'10. .41 dv. 100. Wilkes-Barre, Pa.......June. ' 11. . 42 xxxiv. 101. San Francisco, Cal......Oct.. '11..42 xliv. 102. New York. N. Y.*......Feb 12. .43 Ixxvii. 103. Cleveland, Ohio........0ct;' '12.. 44 wii. 104. New York, N. Y.*......Feb.. '13. .45 xv. 105. Butte, Mont...........Aug., '13. .46 ?' 108. New York, N. Y........Oct., 13..47 vii 107. New York. N. Y.*......Feb.. '14..48 xv. 108 Salt Lake City. Otah Aug. :l. 49 5: 109. Pittsburgh, Pa.........Oct., 14. .50 vii. 110. New York, N. Y.*......Feb., '15. .51 xvi. 111. San Francisco, Cal......Sept., '15. .52 xii. 112. New York,N. Y.*......Feb., '16..54 xvi. 1 Arizona...............Sept.,'l6. .55 VII 114. New York, N. Y.*......Feb., '17: .56 vii. 115. St. Louis, Mo..........Oct.. '17..57 vii. 116. NewYork,N. Y.*......Feb.. '18..59 xvii 117. Colorado.....:........Sept.,'18. .60 vii. 118. Milwaukee, Wis........Oct.. '18. .60 x:!: 119. NewYork,N. Y.*......Feb., '19..61 xi. 120. Chicago...............Sept.,' l9.. 62 VII. 121. New York, N. T.*......Feb., '20..63 ix. 122. Lake Superior District. .Aug., '20.. 66 ix. 123. New York, N. Y.*......Feb., '21. .66 xiii. 124. Wilkes-Barre, Pa...... Sept.. : 21.. 66 xix. 125. New York, N. Y.*......Feb., 22. .67 ix. 126. San Francisco. Cal......Sept.,:22. .68 xxix. 127. New York, N.Y.*.....Feb., 23. .69 xxix 128. Canada...............Aug., '23. .69 xxxv! 128.129. New York, N. Y.*......Feb., ;24. .70 xxxi. 130. Birmingham, Ala.......Oct. 24. .71 xxxiii 131. NewYork.N Y.*......Feb.: '25.. 71 xxxviii. 132. 131.Salt Lake City, Utah .. .Sept., '25. .73 xvi 133. New York, N. Y.*......Feb., '26. .73 xxii. 134. Pittsburgh Pa ....... Oct.. '26. .74 xv. 135. New York,' N. Y.*............Feb., '27. .75 x::: 135.136. NewYork,N. Y.*......Feb., '28..76 104 137 NewYork.N. Y.*......Feb., '29. .291 116 138.San FranciscoYork,N.Y. Cal..........Oct. 29..308 406 139. New York, N. Y.*...Feb., '30..30H 1321

Jan 1, 1930

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By J. J. Beeson

Page I. PrimaRy MineRalization............................................ 356 1. Introduction..................................................... 356 a. Scope of Work............................................... 356 6. Acknowledgments............................................ 357 c. The Bingham Mining District.................................. 357 d. General Geology.............................................. 357 e. The Utah Copper Mine....................................... 376 f. Field and Laboratory work.................................... 376 2. The Quartz-Monzonite.............................................. 377 3. The Pegmatite Veins.....:.•..............................:........ 378 4. The High-Temperiture Veins.........................-.............:379 5. The Early Hydrotherma! Period.:......................'............ 380 6. The Late Hydrothermal Period................................:.... 385 II. Seconuabx EnricuMENT............................................. 386 . 1. Author's Note;..... ;............................................ 386 2. Factors Governing Enrichment.....................................: 387 3. The Enrichment.................................................... 387 4. The Covellite Enrichment.; .:; ; : .:. :..:.............:................ 388 a. The Capping above the Covellite Ores:....:....................... 388 b. Conclusions Drawn. from a Study of the Capping and the Covellite ; Ores....,.............................................:.....,.' 392 c. Covellite Enrichment at Depth......:......................... : : 392 5. The Chalcocite Enrichment...................................... ; 394 a. The Carbonates in the Capping above .the Chalcocite Ores...:..: .. 394 ' b. The Formation of Chalcocite..:.:. :......:..'...........,......' 394 . 6. Secondary Chalcopyrite and Bornite.............................i ..., . 395 111.- Conclusions as to the Formation.oF the ImpoRtant Sulphides in the Disseminated ORes........................................,.......... 400 I. Primary MiNeRalization 1. Intrdtiction a. Scop. e .of Work.. first part bf, this paper deals with the country rock, its pegihatitic, pneumatolytic', and hydrothermal altektions; also, the effect of magnetite on the deposition of the primary chalcopyrite and pyrite.

Jan 1, 1916

By R. Q. Shotts

Nitric acid oxidation rate analyses of three coals, previously studied microscopically by the Bureau of Mines, revealed three components. Relative quantities agree with those found for the four components given by the Bureau and results are consistent with current ideas of coal constitution. Possible multi-component composition for bright coal and a reactivity-rank relation are suggested. THE physically dissimilar components of bituminous coals often are easily recognized mega-scopically. Under the microscope, reflected light or light transmitted through thin sections reveals the presence of the different components, even when these are intimately mixed. Optical methods for the quantitative estimation of the relative abundance of the various components, both by means of thin sections and by particle count, have been fully described.'. ' It has long been recognized that there are chemical and physical differences between the various petro-graphic components of bituminous coals, although analytical differences usually are small.:'. ' Only in the case of fusain have chemical differences been used for quantitative determination of a component. C. C. Hsiao and associates, at the Mineral Industries Experiment Station of the Pennsylvania State College, have described a method of analysis which is based upon the differences in the rate of nitric acid (8N) oxidation, fusain, and the other components of coal."," The reproducibility of their method and its applicability in checking microscopic determinations of fusain content have been supported by several independent investigations.'. " The writer has proposed the use of differences in oxidizability for the estimation of other components." "' The results of the oxidation of whole coals and of float-and-sink fractions of coals were reported. In most cases the plots of the logarithms of the percent dry, non-fusain, organic residue from oxidation, against time, revealed the presence of at least two distinct components. Both components appeared to oxidize according to a first order law, but the reaction constants for the components were distinctly different. One or more of the dull density fractions were found to contain but one component, and some of the lower rank coals oxidized in such a way as to suggest the presence of three components. A suitable way to check the identity and significance of the components delineated by oxidation would be to analyze a sample of coal both by the nitric acid oxidation procedure and by a microscopic method. The writer was wholly unfamiliar with either of the microscopic techniques commonly used, and to make such a comparison it was necessary to rely upon microscopic analyses made by someone else. It is hoped that some laboratory which is equipped to make both types of analyses will some day make them upon identical samples. During the past 20 years, four Alabama coals have been analyzed petrographically and the results published by the United States Bureau of Mines. They are: 1—Flat Top mine, Mary Lee bed; 2—Empire mine, Black Creek bed; 3—Wylam No. 8 mine, Pratt bed, all in the Warrior field; and 4—Soot Creek mine, Fairview bed, in the Coosa field."-" Of these, only the Flat Top mine is still operating. Because of the closing of these mines, it first appeared necessary to rely upon the indirect and unsatisfactory procedure of sampling the beds in other mines located as near to the closed mines as possible. Upon investigation, however, it was found that the Bureau of Mines still had, in storage, the very same samples which had been used in the published petrographic studies. The Bureau very generously furnished about 2000 g each of the Pratt, Mary Lee, and Fairview bed coals, largely lumps but with some fines. The blocks of coal, when received, still were covered by the paraffin coating which had been placed on the polished surface, in the case of the Mary Lee coal almost twenty years ago. Procedure The procedure for oxidizing the coal sample and removing the alkali-soluble humic acid has been described. In the present study, oxidation periods of 1/6, 1/3, 1/2, 3/4, 1, 2, 3, and 4 hr were used. All oxidations were made in triplicate. After the paraffin had been removed in boiling water and the coal washed carefully with cold benzene, the entire sample of approximately 2000 g, obtained from the Bureau of Mines, was crushed to pass a No. 4 sieve. About 200 g of this material was pulverized to pass

Jan 1, 1954

By W. Rostoker, R. P. Elliott, B. W. Levinger

Phase equilibria in the Ti-Mn-Mo system have been investigated in the composition range 100 to 60 pct Ti and in the temperature range 550 to 1150°C. Three out of ten isothermal sections are presented as well as seven vertical sections, projections of the beta space and the surface of incipient melting. A STUDY of the system Ti-Mn-Mo was undertaken as part of a program to aid in the development of titanium-base phase equilibrium diagrams of potential technical importance to alloy development. The scope of the investigation included the composition range 100 to 60 wt pct Ti (all compositions refer to weight percentages) and the temperature range 550" to 1150°C. A surface of incipient melting was constructed from measurements of a large number of alloys. In the binary system Ti-Mo,' the high temperature modification of titanium generally spoken of as the p phase is stabilized to successively lower temperatures with increasing alloy content. There are no known intermediate phases, and complete miscibility exists between body-centered cubic titanium and molybdenum. The u solid solution is limited to less than 0.8 pct Mo at temperatures between 885" and 600°C. An equilibrium diagram for the binary system Ti-Mn has been published.' Manganese behaves as a p stabilizer but undergoes a eutectoid transformation at about 20 pct Mn and 550°C to a plus an intermediate phase. The structure of this phase has been found to be isomorphous with the a phase FeCr." Accordingly, the phase is assigned the formula TiMn, although its actual location on the composition scale has not been determined and may well be not exactly at the equiatomic composition. In disagreement with ref. 2, the origin of the TiMn phase has been shown' to be a peritectoid transformation at a temperature between 900" and 1000°C. A second intermediate phase occurs at the atomic proportions TiMn,. The structure of this phase was originally established by Wallbaum" as having a hexagonal lattice (C 14 type, 12 atoms per unit cell) isomorphous with MgZn,. In this work, the structure determination was confirmed and lattice parameters determined to be: a = 4.815 kX, c - 7.901 kX. Because of the extensive range of the P phase, the ternary system was suited to the determination of the phase boundaries by the parametric method of Andersen and Jette." During the course of the investigation, this method was found applicable only to the P/a+P boundaries but not to P/P+ compound boundaries. Metallographic methods were used alternatively for delineating these phase boundaries. Preparation and Treatment of Alloys Over 70 alloys were prepared for the study of this system. Ten gram alloy buttons were arc melted in a nonconsumable electrode furnace using inert atmosphere protection, and a water cooled copper crucible. The construction and operation of this type of melting unit has been described.' To insure complete solution of alloy additions, especially molybdenum, the buttons were remelted alternately on top or bottom as many as five times. This was accomplished by a suitable mechanism for "flipping" the ingots over. It was very difficult to obtain homogeneous melts in the region of less than 75 pct Ti because of the very high melting point of molybdenum and Ti-Mo master alloys and the comparatively low boiling point of manganese. Thus, the arc conditions for insuring complete solution of molybdenum were incompatible with the prevention of heavy losses of

Jan 1, 1955

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, ' AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.' The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962

By G. P. Boomslitter

In previous discussions on stresses in hoisting ropes, little has been said concerning the effect of the elasticity of the rope itself on the stresses due to acceleration. Laschinger1 has calculated acceleration stresses for several cases but he has ignored the elasticity of the rope as a factor, except as it compresses the drum and stretches itself as it winds thereon. He also deals with steam plants and he shows the effect of the "jerky" start of the engine. This effect would actually be reduced by the elasticity of the cable. With the advent of the motor-driven hoist, new conditions have arisen. The jerk mentioned by Laschinger has been eliminated and smoother starting made possible. But the elastic properties of the rope seem to introduce considerable periodic acceleration stresses in the rope. The following discussion of acceleration stresses is based on the assumption of a constant acceleration at the drum. To be exact, the mathematical work is based upon the assumption that the top is moving upward with a constant acceleration, and ignores the fact that the cable is shortening as it winds. However, the effect of the shortening would be inconsiderable during the first part of the acceleration period. Most hoisting engineers make the assumption of constant acceleration at the drum. Under the older method of calculating acceleration stresses, this would be true with a constant torque motor. But if stresses vary, as this paper attempts to show that they do, constant torque would not give constant acceleration, although the velocity-time curves obtained in the full size test herein described showed that they approach rather closely to this condition, at least as nearly as could be measured. Theoretical Discussion According to elementary physics, the force required to accelerate a Wf body of weight W at the rate of f ft. per sec.2 is wf . To raise the body Wf with acceleration of f ft. per see.2 the total force required is I + Wf, in if

Jan 1, 1927

By R. L., Fullman

During the past year there have been a number of significant investigations that have furnished evidence on the driving forces governing grain growth and on the role played by boundary impurities. Thus Burke has shown that in high purity alpha brass the rate of grain growth in the earliest stages is approximately inversely proportional to the existing grain size. This relation agrees with one derived by Zener assuming that surface energy was the driving force in grain growth. Also in confirmation of the surface energy hypothesis, Burke found that growth virtually stopped when the grain boundaries or even only the grain corners were melted.

Jan 1, 1949

By W. O. Crosby

INTRODUCTION. THE crystalline belt of the Atlantic Seaboard, south of New York, attains its maximum breadth of 220 miles on the northern border of North Carolina; and in this State it is most widely characterized by the occurrence of gold in workable deposits. Half a dozen auriferous belts have been recognized by Nitze and Hanna.1 These are, in the main, coincident in position and trend with the NE.-SW. zones of metamorphic slates and schists, which, more than any other feature, give character to the geological map of North Carolina. The central gold-belts, accompanying the main zone of slates and associated igneous rocks, are much the more important and persistent, and may be regarded as continuous northward across Virginia and southward into South Carolina. Tile eastern belt, on the other band, is the shortest and, economically, one of the least important. Its extreme length does not exceed 25 miles, the narrow band of slaty rocks to which it belongs passing, both NE. and SW., beneath the coastal-plain formations. But, although limited in area and production, this belt is, perhaps, comparable with the central belts or any part of the sea-board crystallines in the variety of conditions under which the gold occurs. It lies chiefly in the NE. part of Franklin county and the NW. part of Nash county, on the watershed of Fishing creek and other tributaries of Tar river. The elevation is between 400 and 500 ft. ; and the Tertiary peneplain has here an exceptionally perfect development, the reliefs separating the slightly incised stream-courses consisting of broad, flat-topped peneplain remnants, bounded by gentle lateral slopes.

Mar 1, 1908