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By William D. Klopp, Joseph R. Stephens

Chromium alloys were coated with silicon, alumi-nuw, and boron by pack cementation. None of these simple coatings provided adequate nitridation/oxida-tion protection for a Cr -0.17pct Y alloy substrate as shown by a substantial Increase in the ductile -brittle transition temperature after air exposure for 100 hr at 2100°F. Iron-modified silicide coatings afforded good protection, holding the transition temperature of air-exposed specimens to 350° F compared to 200° F for uncoated unexposed specimens and 800°F for un-coated exposed specimens. Additional attractive cant-binations of modi-tying elements included Fe-mo, Fe-Mo-W, Fe-,Mo-W-Ti, and V-Mo-W-Ti. THE desirability of increased operating tempera-tures as a mcans of improving the performance of ad-vanced air breathing engines has resulted in emphasis on the development of materials with high operating temperature capabilities. Chromium, because of its relatively low density (7.19 g per cu cm), high melt-ing point (3410°F), and adequate strength upon alloy-ing, is a candidate material for turbine buckets and stator vanes of advanced air breathing engines. How-even, chromium is not without severe limitations, the major one being susceptibility to nitrogen embrittle-ment upon exposure to air at high temperatures.1,2 For example, a 25-hr air exposure of a Cr-5 pct W* * All compositions in wt pct. alloy at 2100°F produces a 600°F increase in the duc-tile-brittle transition temperature.' Although dilute alloying with such elements as yttrium, lanthanum, arid thorium3,4 or strong nitride formers5 has been shown capable of reducing nitrogen embrittlement, it is apparent that some additional form of surface protection, such as coatings or claddings, will be required for long time service in air breathing engines. Studies of aluiminide6 and silicide7 coatings and of nickel-base claddingsl on chromium alloys to date have suggested that these protection systems are inadequate. Of the aluminidc systems Studied,6 a simple aluminum and an Fe-Al coating on a Cr-5 pct W-0.1 pct Y alloy showed the lowest air exposure weight gains. However, the air exposures raised the ductile-brittle transition temperature of the coated specimens to above 1600°F from an initial level in unexposed specimens of about 500°F. A second in-vestigation for protection of Cr-5 pct W-0.1 pct Y employed gas pressure bonded alloy foils as protective claddings.1 An aluminized Ni-20 pct Cr-20 pct W alloy plus an unalloyed tungsten barrier layer gave the best performance with air exposure lives based on appearance and weight gains of over 600 hr at 2100°F. However, the bend ductile-brittle transition tempera-ture was increased to at least 1000°F after 100 hr at

Jan 1, 1970

By J. R. Coulter, F. O. Case, H. G. Satterthwaite, B. Harden

During the two years that the Henderson plant has been in operation, a number of technical improvements have been made by the staff of Basic Magnesium, Inc., the effects of which were realized subsequent to the writing of the paper by Major C. J. P. Ball (p. 28j, this volume). Pellet Mix The process as originally installed required the use of peat moss in the mixture going to the chlorinators. This had to be imported from Canada at a considerable cost, and, besides being expensive, constituted a serious fire hazard in the dry climate of Nevada. Experimentation looking toward its elimination had been going on for some time and was actively pushed as soon as operations commenced. It was found that a pellet mix containing no peat, which would chlorinate at a satisfactory rate, could be cast as a fluid slurry, which would set up into a hard mass having the desired porosity. For carrying out this operation, equipment similar to that used in the manufacture of phosphate fertilizer at Anaconda, Mont., was installed and proved eminently successful. The dry materials, with peat moss and raw concentrates entirely eliminated, are mixed with magnesium chloride solution in two Pratt phosphate mixers and the resultant slurry is poured onto two 48-in. slowly moving rubber conveyor belts. By the time the slurry has reached the head pulley, the material has set su4iciently to be broken and sized as desired. The discharge from the casting belts is fed to the four rotary kilns in the preparation plant, where it is dried and coked to the proper degree for subsequent chlorination. With the peatless feed the capacity of the kilns was found to be about double what it had been before, so that the four rotaries suffice for a 10-unit operation, thus making it unnecessary to operate the extruders and tunnel kilns. In addition to saving the cost of the peat, the new system can be operated with about 85 per cent less labor than was formerly required in the preparation plant. The new pellet production system has also made it feasible to install centralized crushing equipment with suitable conveyors and a loading station. Containers of 8000 lb. capacity were substituted for small cubicles of 1000 lb. capacity which formerly were used for charging the chlorinators, and trailer trucks were substituted for the small trains originally provided for transportation from the preparation plant to the chlorinators. These changes resulted in a considerable saving in handling and transportation charges. Handling Molten Metal The molten magnesium originally was ladled from the electrolytic cells into small gas-fired brick-lined cars standing between the cell rows. From these cars the metal nes ium. into ''cheeses'' weighing from 150 to 300 lb. After solidification the

Jan 1, 1944

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By O. D. Sherby, J. L. Lytton, C. R. Barrett

Randomly oriented polycryslalline copper of 99.995 pcl was tested in tension at temperatures of 626o, 496o, and 406o. The gvain-size mnge investigated was from 0.03 to 0.7 mm. Grain sizes were produced by two techniques: 1) varying the amount of prior cold work and the amealing time at constant annealing temperature so as to obtain various vecrystallized grain sizes with minimum grain growth, and 4 holding the prior cold work constant while varying the annealing time or temperature so as to obtain varying grain sizes by grain growth. Polycrystalline samples (grain size of 0.03 mm) with a strong. [001](100) texture were also studied. The relationship between the steady-state creep rate, Es, and pain size was found to be the same indepentent of the technique used to prepare the various grain sizes. For specimens with grain diameters above about 0.1 mm ea zuas esse)ztiallj~ independent of grain size, while for smaller grain diameters Cs increased slightly with decreasing grain size. Strongly textured polycrystalline copper, which contained low-angle grain boundaries, exhibited steady-state creep rates that were slightly lower than those observed in randomly oriented copper, of the same gain size. The results are explained by conside?%ng- the contribution of grain boundary shearing to the total strain and the effect of grain size on the resulting creep substructure. EXPERIMENTAL observations concerning the influence of grain size on steady-state creep rates are varied and oftentimes conflicting. Numerous early investigators found that an increase in the grain size resulted in a decrease in the high-temperature steady-state creep rate, i,.'-" Other workers have foundthat ef decreases with increasing grain size up to some optimum grain size and then increases with a further increase in grain size.'- '' It has been suggested that es, decreases with an increase in grain size only because the range of grain sizes studied normally lies to the left of the grain size for optimum creep resistance. However, sherbyl2 and Feltham and his co-worker13, 14 have found that even for small grain sizes 2, does not always decrease with an increase in grain diameter but may be proportional to the square of the grain diameter. A possible explanation for the different creep rate-grain size relationships which have been observed is that in most experimental studies different grain sizes have been prepared by annealing at various temperatures. For metals in which the impurity concentration is high (greater than about 0.1 at. pct) this type of

Jan 1, 1968

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By C. S. Barrett, P. Coheur

ANNEALING twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the recrystallization texture,1 and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (111), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3,4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture this is true, for example, with the (113) [211] texture so commonly reported for brass-hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism . MATERIALS AND METHODS The samples investigated were of secondary copper (melted in Belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice has not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip 10 cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a cameral that traversed

Jan 1, 1946

ASDIE from the John Fritz Medal, in which the Institute participates through its representation on the John Fritz Medal Board, the Institute itself has four awards it may make annually, as follows: the Robert W. Hunt Medal and Prize, the J. E. Johnson, Jr., Award, the James Douglas Medal, and the William Lawrence Saunders Medal. Robert W. Hunt Medal and Prize The partners of Robert W. Hunt established a fund which was presented to the Institute at a fitting ceremony on May 27, 1920, to establish an annual medal and a sum of money to be awarded under the following rules: 1. The award shall consist of two prizes: first of a gold medal, second of a sum of money; a certificate to accompany each prize. The money prize shall not be awarded to a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age. In general it will be understood that the Committee shall award the money prize to the younger men, rather than the medal. 2. The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel. The scope of the term "iron and steel" shall be determined by the subcommittee considering the awards. In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition of the fact that Captain Hunt's main contributions to the industry have been in the improvement of production and quality of material. 3. A subcommittee of three to five, including the Chairman of the Iron and Steel Committee, shall be appointed by the Iron and Steel Committee annually to adjudge the award subject to approval. 4. The awarding committee shall submit its report to the Iron and Steel Committee at its October meeting, and the award shall be certified to the Secretary of the Institute in time to permit the presentation to be made at the Annual Meeting of the Institute. 5. The recipient of the award shall be designated "The Hunt Medallist." This prize is administered by the Iron and Steel Division. Awards of the medal have been made as follows: 1920—Robert Woolston Hunt. 1926—Charles Lewis Kinney, Jr. 1928—John A. Mathews. 1929—Edgar Collins Bain. J. E. Johnson, Jr., Award This award is made from the income of a fund of $3000 donated by Mrs. Margaret Hilles Johnson in memory of her husband, J. E. Johnson, Jr., who was a prominent engineer, author of two valuable volumes on iron blast-furnace construction and practice, vice-chairman

Jan 1, 1929

By S. Beatty

RECENT experimental results' on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists' have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

By E. I. Larsen, E. F. Swazy, F. R. Hensel

EXPERIENCE has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. TEST MATERIALS Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It was found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended on the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as one eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from. 900°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal composition was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical properties and certain bearing properties of this alloy are described in the present paper. PREPARATION OF COMPACTS Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition: 25 per cent nickel; 7 silicon; 3 phosphorus; 64 copper. This alloy is brittle in. the cast condition and can be readily powdered. SINTERING PROCEDURE The blended powders were pressed at 25 to 40 tons per sq. in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By G. H. Ruggles

POPULAR opinion, as it might be termed, has always been of the trend that a flotation reagent added to the ball mill during grinding would be more thoroughly mixed with the pulp and for that reason more effective in the production of low tailing. That there are other effects, inimical to good flotation, when using so-called chemical reagents, is brought out by the series of tests outlined in Table 2. It was defi-nitely proved that if either the T. T. mixture (20 per cent thiocarbanalid-80 per cent orthotoluidin) or po-tassium xanthate were added to the ball mill the result-ing flotation concentrate would be lower in copper and higher in insoluble than the concentrate produced by adding these same reagents without the ball mill cir-cuit. With the T. T. mixture four sets of tests were made. The screen analyses of the flotation feed show that there was very little difference in the original grind-ing. When the T. T. mixture was added to the head of the flotation machine the flotation concentrate had a little over 61 per cent solids -200 mesh. If the mix-ture was put into the ball mill the flotation concentrate had but 40.7 per cent of the solids -200 mesh for one set of tests, and 49.0 per cent for the other set. With the mixture at the head of flotation the total concen-trate was high in copper (34.715 and 36.525 per cent) and low in insoluble (13.20 and 11.61 per cent). The assay of the concentrate when the T. T. mixture was introduced into the ball mill was what might be termed low in copper (29.389 and 30.833 per cent). In one of these 'sets of tests (periods 8 to 11, third column) the insoluble was high, 16.81 per cent. The other run (peri-ods 12 to 15, fourth column) for some unknown reason shows a low insoluble, 12.72 per cent. With similar grinding the addition of potassium xan-thate to flotation produced a concentrate having 62.8 per cent -200 mesh, whereas with the potassium xanthate added to the ball mill the flotation concentrate was very coarse, only 36.4 per cent passing 200 mesh. The difference in the total assay of the concentrate is remarkable ; 35.847 per cent copper when the xanthate went to flotation and 30.44 per cent copper when the xanthate was added to the ball mill; insoluble, 10.94 per cent in the former instance, as 22.15 per cent in the latter.

Jan 8, 1927

By C. S. Barrett, P. Coheur

AXnealing twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the re-crystallization texture,' and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (III), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3'4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture— this is true, for example, with the (113) [ZII] texture so commonly reported for brass—hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism. Materials and Methods The samples investigated were of secondary copper (melted in belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice have not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip I. cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a camera2 that traversed

Jan 1, 1947

By A. K. Jena, M. O. Bever

The thermodynamic behavior of dilute solutions of copper, silver, and gold in liquid tin is not explained by current solution theories.1-3 The relative partial gram-atomic enthalpies, or heats of solution, of silver, gold, and platinum in liquid lead at 623°K have been measured in the investigation reported here. Their interpretation requires a modification of the regular-solution theory although lead-rich solutions may be expected to be simpler than tin-rich solutions. The liquid metal solution calorimeter used has been described.4 At the start of a run the bath consisted of 621 g of reagent-grade lead. Several calibrating additions of lead were made during a run; a value of 3.48 kcal per g-atom5 was taken for H623°K - H273°K Two runs were made with each of the solutes silver, gold, and platinum. Annealed wire samples of 99.999+ pct purity were used. Four to six samples each weighing 0.5 to 1,0 g were added from 273°K to the bath at 623°K and the associated heat effects were measured. The samples dissolved in approximately 3 min. No serious experimental difficulties were encountered. The heat effects of the additions in a run plotted against the average atom fraction of solute before and after each addition314 were linear functions of the concentration in lead of silver, gold, and platinum, respectively. By subtracting the difference between the heat contents of a solute element at 623° and. 273°K5 from the measuredheat effects, the partial gram-atomic enthalpy relative to the solid solute was obtained. The relativ: partial gram-atomic enthalpy at infinite dilution and the concentration dependence of the partial gram-atomic enthalpies obtained from the plots of vs atomic fraction x are listed in Table I. The relative partial gram-atomic enthalpy at infinite dilution of silver in lead of 5.46 kcal per g-atom at 623°K compares with values at 723°K of 5.74' and 5.765 kcal per g-atom. These data yield a temperature coefficient of 3.0 cal per g-atom-OK. The partial gram-atomic enthalpy at infinite dilution of gold in lead at 623°K is 0.89 kcal per g-atom compared with 0.85 kcal per g-atoms (obtained by extrapolation) and 0.95 kcal per g-atom.5 By combining these values for 623°K with those for several other temperatures5" the temperature coefficient of was found to be 3.2 cal per g-atom-OK. No thermodynamic data are

Jan 1, 1968

By C. S. Barrett, P. Coheur

AXnealing twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the re-crystallization texture,' and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (III), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3'4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture— this is true, for example, with the (113) [ZII] texture so commonly reported for brass—hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism. Materials and Methods The samples investigated were of secondary copper (melted in belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice have not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip I. cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a camera2 that traversed

Jan 1, 1947

By D. C. Hilty, W. Crafts

The solubility of oxygen in iron containing aluminum has been determined at 1550°, 1600°, and 1650°C and found to be much higher than predicted from theoretical considerations, possibly due to equilibria with an iron-aluminum spinel phase rather than pure AI,O.. The presence of manganese greatly increased the deoxidizing power of aluminum. DEOXIDATION and inclusion formation in steel have proved to be elusive phenomena that are difficult to control in spite of much effort to understand and evaluate the reactions. Study of the problem indicated that more accurate data on the solubility of oxygen in iron containing deoxidizers were essential to further progress, and an empirical determination of oxygen solubilities has been initiated at the Union Carbide and Carbon Research Laboratories, Inc. The investigation has included the effects of aluminum, silicon, manganese, and combinations of these elements at 1550°, 1600°, and 1650°C. The equipment and experimental procedure as well as the results of a study of the effects of aluminum are described below. In general, it was found that the solubility of oxygen in iron containing aluminum is much higher than predicted, possibly because of the formation of complex nonmetallic phases, and that manganese greatly increases the deoxidizing power of aluminum. The generally accepted deoxidation curves for 1600°C are summarized in fig. 1, from "Basic Open Hearth Steelmaking"'. These curves are assumed to represent the solubility of oxygen in the presence of deoxidizers and should indicate the limits of mis-cibility gaps in the phase diagrams of the systems that control the formation and character of non-metallic inclusions as described by Benedicks and Lofquist'. They were derived mainly by application of the methods of thermodynamics to the available experimental observations, and by calculations based on the thermal constants of the pure substances when experimental data were lacking. Among the more notable researches contributing to the development of knowledge of oxygen solubilities are those of Korber and Oelsen8, 4, C. H. Herty, Jr. and associates5,6, Krings and Schackmann7, Went-rup and Hieber8 Schenck and Briiggeman9, Vacher and Hamilton'" and Chipman and co-authors 1,11,12,13 Practically, the deoxidation curves are of limited value in predicting oxygen content and rationalizing deoxidation practices. The reasons for this inadequacy appear to be error from inaccurate data, oversimplifying assumptions, interacting effects of combined deoxidizers, and possibly unknown extra-equilibrium and side reactions. Although inclusion formation is a very complex reaction it must be re-

Jan 1, 1951

By W. H. HOWARD

Discussion of the paper of W. H. HOWARD, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin No. 92, August, 1914, pp. 2029 to 2046. EDGAR M. DUNN, Anaconda, Mont.-Mr. Howard's contribution to the literature on the Cottrell, method. of electrostatic precipitation of flue dust and fume at Garfield has been read by us with peculiar interest for the reason that we have been experimenting with the same process at Anaconda for the past eight or nine months, with a view to adapting it, under the direction of Dr. Cottrell and the supervision of J. 0. Elton. and D. R. Kellogg, representing the Anaconda Smelter Commission, to the treatment of very large volumes of gases, using large pipe treaters and various forms of electrodes, with about 150,000 volts rectified current. For the amount of gas to be treated here the 5-in. pipe means a cost for installation that is practically prohibitive, clue to the tremendous number of pipes required, and we have been trying to cut installation costs by increasing the size of the pipes. All of our work is still in the experimental stage, but we have obtained good clearance on our mixed roaster and converter gases with a 3-ft. pipe treater 20 ft. long, and with 5 ft. velocity therein; and with a discharge electrode of a single No. 29 nichrome wire set in the middle of the 3-ft. pipe, with. a consequent electrode spacing of 18 in. The current used has been 150,000 to -160,000 volts, .and of course there have been troubles galore, relating particularly to insulation and rectifying. Blast-furnace gases did not give so good clearance, probably due to relative poverty in moisture and S03 content of blast gases to roaster-converter gases; making the blast gases the poorer in conductivity. Our experience has been so satisfactory that in our next experimental plant-built on a somewhat larger scale-we shall attempt a 4-ft. treater with greater electrode spacing, and a somewhat higher voltage-up to 220,000. As to fractional precipitation, mentioned by Mr. Howard, this idea was tried out at Anaconda last year (1913). Formerly our furnaces (Bruntons) roasting flue dust for the recovery of white arsenic, passed so great an, amount of dust to the settling kitchens that refining of this arsenical product was necessary to eliminate the 5 to 20 per cent. dust contained therein. Consequently the manufacture of As203 was effected in two stages, with a reverberatory roast of the first .product to obtain the final 99.5 per cent. As203. -

Jan 11, 1914

SEC. 1. This Institute is incorporated under the Membership Corporations law of the State of New York; its corporate name is American Institute of Mining and Metallurgical Engineers, Inc.; and its objects are such as are stated in its Certificate of Incorporation. ARTICLE II SEC. 1. The membership of the Institute shall comprise four classes, namely: 1. Members; 2. Honorary Members; 3. Associates; 4. Junior Associates. All members shall be equally entitled to the privileges of membership, excepting that Honorary Members, Junior Associates, and Members and Associates whose residences shall be outside of the United States, Mexico, and Canada shall not be entitled to vote. Members and Associates residing within the United States of America, Mexico, and Canada, and not in arrears for dues, shall be entitled to vote in person at the meetings of the Institute, or, as hereinafter provided for, by letter ballot. SEC. 2. Members shall comprise all those persons who on the third Mon- day of February, 1918, were members of the Institute, and in addition thereto, all those thereafter elected or transferred into the class of Members. A person to be eligible for election or transfer into the class of Members must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. Graduation from the scientific course of a college, approved by the Committee on Membership, shall be considered equivalent to two years' employment, as required in the previous sentence. Employment as a teacher of engineering, mining, geology, metallurgy or chemistry, if in direct charge, may be considered a position of responsibility as specified in the second paragraph. Persons employed in research or any scientific literary work or in teaching in the scientific departments of colleges, approved by the Committee on Membership, who at the same time are engaged in consulting or in the active practice of mining, geology, or metallurgy, shall be entitled to consider the time so spent in active practice as equivalent to an equal length of time of employment in positions of responsibility, provided the work done or the positions held seem to the Committee on Membership to warrant the equivalency. The requirement of three years' employment in positions of responsibility may be waived by the Committee on Membership in the case of persons who have done notable original work in mining, or metallurgy, or have won distinction by research or investigations In one or more of these subjects.

Jan 1, 1928

By Frederic Lahee

THE total production of crude oil in Texas during 1924 was said to be 133,613,985 bbl. as compared with 125,991,628 bbl. in 1923.1 Subtracting from these figures the yield of the Gulf Coast fields, there remains, for the other part. of Texas, a yield of 106,272,573 bbl. in 1924, as compared with 101,931,595 bbl. in 1923. This represents an increased, production of over 4,250,000 bbl. for all of Texas outside of the Gulf Coast or Salt Dome fields. Within this same region, in 1924, there were 3624 completions, of which 2352 were oil or oil and gas wells, 7 were gassers, and 1265 were dry holes. Thus, nearly 35 per cent. of the completions were dry holes. In 1923, there were 4134 completions, with 2853 oil or oil and gas wells, 2 gas wells, and 1279, or 31 per cent. of the total, dry holes. Outside of the Gulf Coast region, six major pools were discovered and developed in 1924.; two pools, previously discovered, were extended far beyond their limits at the end of 1923, and many smaller pools were opened. The major pools were the Big Lake field, in Reagan Co., the New Richland field, in Navarro Co., the Harmel, Carey, and Ragle pools, in south Archer County, and the Wortham field, in Freestone and Limestone Counties. Fields that were notably extended were the Panhandle producing area and the Luling field. Many wildcat wells have been drilled; most -of these were failures, but several opened .pools and several have had sufficiently favorable results to. lead to further drilling. The activity of the operators in searching for new production was very intense during 1924, and indications point to as feverish a campaign during the coming year. This will be stimulated by rising prices for crude oil. There are good reasons for believing that new pools will be discovered along the Mexia fault zone, in Archer, Young, Baylor, and Throckmorton Counties, in the great central region of Texas where we now have the Mitchell County and Reagan County pools, and very likely in the eastern Red River Counties including Cooke and Grayson. On the other hand, with the opening of the year, there is no new big pool in sight. An outstanding feature of the production end of the business is the increasing reliance placed on geological work and geological recommendations. Not in five or six years has there been such a demand for first-class geologists.

Jan 3, 1925

By Henry Siegmann

HISTORY OF PRODUCTION AND USE In 1899 the consumption of fluorspar in the United States was reported as 16,000 tons. The invention of the open-hearth method of steel manufacture, plus the beginnings of a fluorine chemical industry, pushed consumption of fluorspar to 250,000 tons by 1918. In contrast to these consumption statistics of the past, the most recent statistics available (1972) indicate a total fluorspar usage in the United States of 1.352 million st (Table 15.4D.1). Fluorspar remains the world's cheapest source of fluorine, and its unique properties make the mineral the most desirable fluxing agent for steel refining. The linking of fluorine with carbon in the late 1930s resulted in the production of fluorocarbon, and constant growth in production over the years has formed the backbone of a strong fluorine chemical industry. For example, in 1972 it is estimated that total fluorocarbon production amounted to 2.113 million tons, and that, in this process, over 1.351 million tons of acid-grade fluorspar was consumed. The producers of primary aluminum long have been concerned about the fast dwindling reserves of natural cryolite. They found the solution to their problem by utilizing fluorspar for the manufacture of synthetic cryolite and aluminum fluoride. Nuclear weapons, as well as the growing number of peaceful uses for atomic reactors, constitute a market for uranium hexafluoride. This chemical and chlorine pentafluoride, used as an oxidizer with rocket fuels, are products that are as much a novelty as fluorocarbons were 25 years ago. Judging from past success in the field of fluorine chemistry research, it is safe to assume that the market for these chemicals will grow in the future. Three major industries account for the bulk of the fluorspar consumption: steel refining, fluorine chemical, and primary aluminum production. These industries have had a pattern of fabulous growth in the past, and their future plans point to a continuation of this pattern. It seems logical that the fluorspar usage also should continue its upward trend. Considering the growth of the fluorspar industry since 1899, and the obvious dependence on imports of fluorspar as a raw material, one of the most puzzling aspects of the past has been the apparent lack of coordination between fluorspar production and fluorspar consumption. A few authoritative voices have spoken out concerning the need to expand fluorspar production in order to meet consumption of the future. During World War II, the U.S. Government took positive steps in this direction by authorizing purchases at attractive prices for its "stockpile program." As a consequence, new fluorspar producing facilities were built, not only in

Jan 1, 1976

ARTICLE I NAME AND OBJECT SEC. I. This Institute is incorporated under the Membership Corporations law of the State of New York; its corporate name is American Institute of Mining and Metallurgical Engineers, Inc.; and its objects are such as are stated in its Certificate of Incorporation. ARTICLE II MEMBERS SEC. 1. The membership of the Institute shall comprise four classes, namely: 1. Members; 2. Honorary Members; 3. Associates; 4. Junior Associates. All members shall be equally entitled to the privileges of membership, excepting that Honorary Members, Junior Associates, and Members and Associates whose residences shall be outside of the United States, Mexico, and Canada shall not be entitled to vote. Members and Associates residing within the United States of America, Mexico, and Canada, .and not in arrears for dues, shall be entitled to vote in person at the meetings of the Institute, or, as hereinafter provided for, by letter ballot. SEC. 2. Members shall comprise all those persons who on the third Monday of February, 1918, were members of the Institute, and in addition thereto, all those thereafter elected or transferred into the class of Members. A person to be eligible for election or transfer into the class of Members must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. Graduation from the scientific course of a college, approved by the Committee on Membership, shall be considered equivalent to two years' employment, as required in the previous sentence. Employment as a teacher of engineering, mining, geology, metallurgy or chemistry, if in direct charge, may be considered a position of responsibility as specified in the second paragraph. Persons employed in research or any scientific literary work or in teaching in the scientific departments of colleges, approved by the Committee on Membership, who at the same time are engaged in consulting or in the active practice of mining, geology, or metallurgy, shall be entitled to consider the time so spent in active practice as equivalent to an equal length of time of employment in positions of responsibility, provided the work done or the positions held seem to the Committee on Membership to warrant the equivalency. The requirement of three years' employment in positions of responsibility maybe waived by the Committee on Membership in the case of persons who have done notable original work in mining, geology, or metallurgy, or have won distinction by

Jan 1, 1925