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Arthur Jarman, Sydney, New South Wales, Australia (communication to the Secretary*):—All designs for modern metallurgical and chemical laboratories should provide each student's desk with a hood or cupboard for the removal of fumes, but I doubt the advisability of placing air-baths and similar apparatus close to the hot plate. It seems to me that unless the draft be exceptionally strong the fumes from ordinary wet assay work will corrode the iron-work of the fittings, in which case the baths would have to be removed to a general desk in order to lighten the work of the laboratory attendant. Since the laboratory described by Mr. White has been in use for two years, I should like to ask if any inconvenience has resulted from this corrosion. If not, it is certainly an important improvement to have the air-baths and similar apparatus placed on the student's desk. The hoods described by Mr. White are supplied with a good draft by means of a fan, which gives them a great advantage

Jan 1, 1905

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.' Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-'. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By W. A. Backofen, D. Lee, F. S. Jabara

THE empirical character of plasticity analysis insures a continuing need for measurements of the yield surfaces of anisotropic materials. Recently, Wheeler and Ireland (W-I) proposed that an octahedral yield locus could be constructed on the basis of six Knoop hardness indentations. Such simplicity would have obvious appeal, if it led to consistently dependable results. In other recent work, a much more straightforward (and more tedious) method of measurement was used to establish all quadrants of the plane-stress yield loci for two substantially anisotropic titanium alloys.2,3 The same materials have since been reex-amined by the W-I method with results being reported here. A full description of the stress state under a Knoop indentor would be complex. In principle, however, this can be avoided in relating the hardness number to a plane-stress yield locus, by the expedient of superimposing the appropriate hydrostatic component on that state of stress. Six possible orientations of in-dentor on orthogonal (symmetry) planes, along (principal) coordinate directions, are illustrated in Fig. 1(0). Pictured in Fig. l(b) are normal-stress components nominally associated with indentation n: o2(H), directly proportional to the Khn in this case, together with By overlaying a hydrostatic tension, ah, that in general is equal to the stress state around the indentation is reduced to one of plane stress in the x-y plane for which the stress ratio is a The key step in the W-I yield-locus construction is to represent the Khn for any indentor orientation as a vector quantity on the octahedral plane. In the plotting, the vector is given as deviatoric stress components along the principal axes in the ratio , where represents the direction of the minor (width) diagonal and 1 that of the major (length) diagonal. There is no attempt by W-I to justify the 7/1, although it might be supposed that the value originates in the usual ratio of major to minor diagonals in a Knoop indentation of about 7/1. If that were its origin, the link to the deviatoric stress ratio would presumably be made by first taking 7/1 and then turning to the Levy-Mises equation for isotropic material: Interpreted in this way, the W-1 approach seems arbitrary and even contradictory. Yet it would still be favored by two circumstances: the deformation under a Knoop indentor approaches plane strain: when dcw/del =a; and the shape of the locus where plane strain is represented is not overly sensitive either to the exact value of dc,/dcl or to the degree of anisotropy, within a rather wide range of both variables. The second point is illustrated below, after a few additional comments on applying hardness

Jan 1, 1968

By D. T. Camp, J. A. Clum

WITH experience, the indexing of back-reflection Laue patterns for cubic crystals is usually a straightforward matter. However, for noncubic systems where in general tables of interplanar angles are not available or when inexperienced personnel are involved, properly indexing a crystal is normally a tedious, time-consuming affair. The authors have written a digital-computer program which calculates and prints out a table of interplanar angles for an arbitrary crystal structure and then systematically searches through this table attempting to obtain a consistent fit to back-reflection Laue data supplied by the user. Of course it is possible simply to calculate a desired set of interplanar angles should this be the only requirement. The program was originally written in ALGOL for use on a Control Data G-21 computer and a preliminary version is described elsewhere.' A version in FORTRAN TV which has been run on an IBM 7040 and one in FORTRAN II run on an IBM 1620 are also available. While it is not the purpose of this communication to describe the program in detail, an indication of how the program operates may help one to decide whether the program would be useful under particular circumstances. The hypothetical example chosen involves the indexing of the zinc crystal which has a hexagonal structure and a c/a ratio of 1.856. Input data for this example consists of only nine cards: The first card controls the list of families of planes to be considered. If the Miller indices of a prospective family are (h k 1), the first digit places a limit, in this case 3, on the absolute values of any individual index. The second digit limits the sum (h +k + l + 1), in this case to 5. Therefore the families (013) and (112) are considered but the family (122) is not. All systems, including the hexagonal, are treated using three-digit Miller indices. The second card contains the crystallographic parameters required to define the system. The first digit is 0 if the system is rectangular, that is all angles are 90 deg. If the system is nonrectangular, as in this example, the digit 1 so indicates. The next three values are the lengths of the sides of the reference cell, a, b, c. The final three entries on the card are the angles, a, 8, y between the sides. The digit 0 on the third card indicates that more data follows, the digit 6 shows that a set of six planes is to be indexed, and the value 2.0 indicates that agreement between a tabulated angle and an input angle is considered adequate if their absolute difference is less than 2 deg. The fourth card lists the measured input angles. a12 = 38 deg, a13 = 24 deg, and so forth. More input angles are listed on cards five to eight with the latter giving the input angle 058 = 40 deg. The final card in this series indicates by the digit 1 that no more data is to be processed. The program operates in the following manner: 1) The input data from cards 1 and 2 is read, thereby indicating the crystal system to be examined and the crystallographic parameters of the particular crystal to be indexed. 2) A table of interplanar angles is generated. 3) The input angles contained on cards 4 to 8 are read. 4) The measured input data is systematically compared with the generated table of standard angles. All combinations of poles whose interplanar angles compare with the requisite, specified accuracy are printed out. If no adequate fit is found an indication of this is printed. A typical line from the generated table of interplanar angles is: (001) - (111) 74.92 64.99 It can be shown that in the Miller-Bravais system the first value corresponds to the angles between (0001)-(1121) and the second to that between (0001)-(1011). This particular set of data gave the following result for the planes 1 to 6: (011) (110) (121) (111) (112) (010) The ALGOL version also has the option of simply providing the Greninger-chart coordinates ? and 6

Jan 1, 1967

By AIME AIME

NOTWITHSTANDING the metropolitan appearance of M. L. Haider, the present Chairman of the Petroleum Division, he is not a native New Yorker, but was born at Mandan, N. Dak., Oct. 1, 1904. He began his travels at an early stage in life and after attending the University of Southern California for two years he spent two additional years at Stanford University and was graduated in 1927. After a few months as an analytical chemist for the Portland Cement Co. he became research engineer in the natural gasoline department of the Richfield Oil Co. where he remained for approximately two years before taking a position with the Carter Oil Co. in Oklahoma. He was chief engineer for this company for three years before being trans-

Jan 1, 1945

By R. I. Jaffee, H. R. Ogden

AT the present time, there appear to be two conflicting opinions on the solubility of boron in titanium. P. Ehrlich' has indicated from X-ray diffraction work that boron is soluble in titanium up to TiB0.8 (17.8 wt pct, 44 atomic pct). The X-ray diffraction pattern for titanium was found in compositions up to TiB0.05_0.07 (1.1 to 1.6 wt pct); then, without a phase gap, superlattice lines appeared up to TiB0.8 On the other hand, Craighead, Simmons, and Eastwood' have estimated the solubility of boron in both alpha and beta titanium to be less than 0.1 wt pct, based on results of metallographic analysis. In some recent work done at Battelle, results were obtained which shed more light on the titanium-rich end of the titanium-boron system. Iodide-type titanium and high-purity crystalline boron were used in this investigation. The boron was prepared by hydrogen reduction of boron tri-bromide and deposition on a hot tungsten wire. The alloys were prepared by arc melting in an argon atmosphere of 10 cm Hg pressure on a water-cooled copper hearth. The ingots were hot rolled to strip at 850°C. Alloys containing up to 1 pct B could be hot rolled. Those containing 2 pct or more B could not be hot rolled. Metallographically, it was found that a second phase was present in alloys containing as little as 0.4 pct B, and that the quantity of second phase increased with increasing boron content. This is illustrated in Figs. la and lb, which show the microstructures of a Ti-0.4B and a Ti-1B alloy annealed in argon at 850°C. X-ray diffraction patterns of alloys containing 1 and 5 pct B revealed the presence of extra lines which correspond to the superlattice lines reported by Ehrlich.' However, no evidence was found of a shift in the lattice constants of alpha titanium indicating that there is very little, if any, solubility of boron in alpha titanium. This fact, coupled with the fact that the alloys were definitely two-phase, indicates that the extra lines are not superlattice lines, but are more probably the result of a second phase of a hexagonal structure almost identical in cell

Jan 1, 1952

By J. T. Mackenzie

Henry Marion Howe, in whose memory we are gathered together, was one of the great thinkers who develop from time to time to whom is given the rare gift of synthesis. Analysis is given to few, but synthesis, the ability to show the relation of all parts to each other and thus to give a clear picture of the whole, is reserved for the very few. Analysis can be achieved by honesty, intelligence, and industry, but synthesis is only given to genius. Professor Howe's crowning achievement is the picture of the whole iron-carbon series shown in Fig. I, which places steel, malleable, gray iron, mottled and chilled irons in their proper relation to each other and shows the essential unity of the series. Perhaps his best statement of the case is found on page go of the Metallography of Steel and Cast Iron in these words: " Each member of the gray cast-iron series consists of the metallic matrix approximately equivalent to that member of the steel-white-cast-iron series to which it corresponds in percentage of combined carbon with its continuity broken up—by masses of graphite ..." Apparently he had taken considerable interest in this idea around the turn of the century, for he refers to a discussion at the Franklin Institute in I900 in which he said: "Though many others had probably conceived this relation between the steels and cast irons, it was here enunciated for the first time, so far as I know. It was received with great incredulity." The concept was explained in some detail in a paper on "The Constitution of Cast Iron" presented before the A.S.T.M. in 1902 when Professor Howe was retiring president of that young society. In the discussion Dr. Sauveur stated that he was "very well acquainted with Professor Howe's theory of the constitution of cast iron," and went on to say that while he "shared it to the fullest extent, some foundrymen . . . claim cast iron is a metal entirely different from steel . . . that steel and cast iron have very little in common, and that therefore the knowledge gained in the study of steel is of little or no value in the study of cast iron." Dr. Moldenke, in discussing the same paper, said he had been working on the same theory for 12 years but he laid no claim to publication. Discussing the difference in the micro-structure of the metallic matrix, Professor Howe pointed out that "such minor structural differences are indeed to be expected, because of the difference in the conditions under which these constituents are generated. "One difference in these conditions is that the steel of most micrographs has been either forged or at least treated thermally in such a way as to give a new structure radically different from that which formed during the initial solidification, whereas the cast irons have not. Hence what we see in the steels is a transformation structure, but in the cast irons a solidification structure. By giving the cast

Jan 1, 1944

By J. T. Mackenzie

Henry Marion Howe, in whose memory we are gathered together, was one of the great thinkers who develop from time to time to whom is given the rare gift of synthesis. Analysis is given to few, but synthesis, the ability to show the relation of all parts to each other and thus to give a clear picture of the whole, is reserved for the very few. Analysis can be achieved by honesty, intelligence, and industry, but synthesis is only given to genius. Professor Howe's crowning achievement is the picture of the whole iron-carbon series shown in Fig. I, which places steel, malleable, gray iron, mottled and chilled irons in their proper relation to each other and shows the essential unity of the series. Perhaps his best statement of the case is found on page go of the Metallography of Steel and Cast Iron in these words: " Each member of the gray cast-iron series consists of the metallic matrix approximately equivalent to that member of the steel-white-cast-iron series to which it corresponds in percentage of combined carbon with its continuity broken up—by masses of graphite ..." Apparently he had taken considerable interest in this idea around the turn of the century, for he refers to a discussion at the Franklin Institute in I900 in which he said: "Though many others had probably conceived this relation between the steels and cast irons, it was here enunciated for the first time, so far as I know. It was received with great incredulity." The concept was explained in some detail in a paper on "The Constitution of Cast Iron" presented before the A.S.T.M. in 1902 when Professor Howe was retiring president of that young society. In the discussion Dr. Sauveur stated that he was "very well acquainted with Professor Howe's theory of the constitution of cast iron," and went on to say that while he "shared it to the fullest extent, some foundrymen . . . claim cast iron is a metal entirely different from steel . . . that steel and cast iron have very little in common, and that therefore the knowledge gained in the study of steel is of little or no value in the study of cast iron." Dr. Moldenke, in discussing the same paper, said he had been working on the same theory for 12 years but he laid no claim to publication. Discussing the difference in the micro-structure of the metallic matrix, Professor Howe pointed out that "such minor structural differences are indeed to be expected, because of the difference in the conditions under which these constituents are generated. "One difference in these conditions is that the steel of most micrographs has been either forged or at least treated thermally in such a way as to give a new structure radically different from that which formed during the initial solidification, whereas the cast irons have not. Hence what we see in the steels is a transformation structure, but in the cast irons a solidification structure. By giving the cast

Jan 1, 1944

The Gooseberry Mine is located 38 krn (24 miles) by road east of Reno, 13 km (8 miles) south of Interstate 80. The mine was originally discovered in 1906 and remained in the control of the Martin family of Fresno, who worked the-property with Mexican ranch hands for 68 years. Westcoast took over the property in 1976 from Apco Oil Corporation. During the time the Martins operated the mine, a 305 m (1,000 ft) inclined shaft was sunk with drifts developed on eight levels exceeding a total of 3,000 m (9,000 ft) in length. It is interesting to note that for over one -half century all development ore was stockpiled. West- coast, the United States mining subsidiary of Home Oil Company Ltd., Calgary, Alberta, completed sinking another vertical shaft to the 396 m (1,300 ft) level. Development work between 122 m and 305 m (400 ft and 1,000 ft) levels has proved the existence of a fine ore body over 300 m (1,000 ft) long. The silver-gold ore grade is fairly consistent in the vertical section, but copper, lead and zinc may show slight increases with depth. Average width of the ore bearing portion of the vein is 2.5 m (8.3 ft). Stoping is by cut-and-fill method. Average silver values within the ore zone have increased from the 152 m (500 ft) level to the 305 m (1,000 ft) level, although the gold values do show some decrease. It is not possible for the geological staff to predict the depth of the ore. However, several years of ore reserves have been proved in the existing mining areas. Important ore minerals are argentite, native gold, and electrum. Trace amounts of galena, chalcopyrite, and sphalerite are associated with the precious metal mineralization. The vein is mainly composed of calcite and quartz. Mine-run underground ore is dumped from the hoisting skip into a coarse ore bin followed by a jaw crusher, an impact crusher, and a 600 mt (650 st) fine ore bin. The mill has a capacity of 317 mt per day (350 st per day). Two-stage grinding is done by a rod mill followed by cyclones with the underflow sent to a ball mill in closed circuit with the cyclones. Cyclone overflow after conditioning receives a primary float in four 1.7 cu m (30 cu ft) cells and a second stage of conditioning ahead of 24 0.8 cu m (30 cu ft) secondary flotation cells. No cleaning stages are used. Flotation tailings are cycloned for a sand-slime separation with the sands used as underground stope fill and the slime portion to tailing dam storage.

Jan 1, 1981

By Luis Emylnn Salas

If the ordinary wet method be attempted for silver-bullion containing tin, much trouble is experienced, varying with the amount of tin present. Even with a percentage as low as 0.05, the end-point is masked by a persistent turbidity, while with amounts ranging from 0.5 per cent. upward, the determination of the exact end-point is impossible, owing to the finely divided or colloidal metastannic acid resisting all efforts to cause it to settle, or to give a clear supernatant liquid. The object of the following experiments was to seek a remedy for these difficulties, and to find the conditions whereby the Gay Lussac method might be applied directly to these bullions. Material containing tin is met with frequently in bullion from Mexico or Bolivia; and tin is carried (sometimes in large quantities) in jewelers' sweeps. 1. A bullion was prepared containing Ag, 74; Cu, 25; and Sn, 1 per cent. A weighed amount was treated by the humid assay-method as if it were an ordinary bullion free from tin. Ten cc. of HNO, (1.21) was added, and the bottle was heated until all traces of

Jan 1, 1913

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,' but neglected one2' which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By Charles M. Packer, Oleg D. Sherby, Roy H. Johnson

Originally round tensile specimens of a eutectic Zn-A1 alloy develop elliptical cross sections during superplastic deformation. This observation, coupled with a detailed study of the microstructure and preferred orieniation, suggests that crystallographic slip and continuous grain boundary migration or re-crystallization are important processes during super-plastic deformation. In spite of the extensive activity in superplasticity1-15 and the numerous explanations proposed, no single model has had universal acceptance. It has been established, however, that the general requirements for superplastic extension of two-phase alloys include an extremely fine, stabilized grain size of the order of a few microns, a temperature about equal to or greater than one-half the melting point, a critical range of strain rate, and a similarity in the mechanical strength of the major phases. The proposed models can perhaps best be characterized in terms of the important phenomena associated with them. These phenomena include: phase instability,1 diffusional creep by volume diffusion3 or grain boundary diffusion4,5 slip and continuous grain boundary migration or recrystalliza-tion,= grain boundary Sliding,7-9,13,14 and dislocation glide.'5 In this paper, experimental observations will be reported which support a model involving slip and continuous grain boundary migration or recrystalliza-tion. Specifically, a correlation will be made between this model and the development of elliptical cross sections as originally round specimens are superplas-tically deformed. For the most part, superplasticity studies have been conducted with eutectic or eutectoid alloys. Probably the most thoroughly studied material has been the monotectoid Zn-A1 alloy.1,2,6,12,13,15 No attention to the eutectic Zn-A1 alloy has previously been reported, and the results discussed in this paper represent part of a general study of the superplastic properties of this alloy. MATERIALS The alloys used in this investigation were prepared by melting appropriate quantities of 99.99+ pct A1 and 99.999 pct Zn in air, mixing, and pouring into a water- cooled stainless-steel mold. Wet-chemical analysis was conducted with each heat of alloy prepared, using the procedure of Fish and smith.16 The composition of the eutectic alloy was 95.1 wt pct Zn. Ingots about 2 in. thick were rolled to 0.4-in. plate at about 300°C with a reduction of 5 to 10 pct per pass. Specimens were machined from the plate with the tensile axis parallel to the rolling direction. The specimens were round, with 0.150-in.-diam, 1.25-in.-long gage length, and 0.25-in.-diam threaded grip sections. EXPERIMENTAL PROCEDURE Specimens were mounted inside a uniform-temperature quartz tube which was surrounded by a double elliptical radiant furnace with a 12-in.-long uniform-temperature hot zone and a low thermal capacity. The tube extended through the top and bottom of the furnace and permitted rapid quenching of the loaded specimens when quickly filled with cold water at the conclusion of the test. The quench precluded any effects on specimen microstructure from a normal, slow cool. Constant stress was applied to test specimens by suspending a load on a constant stress cam of the type described by Hopkin.17 The design of this cam permitted application of a constant stress for elongations up to 200 pct. For greater elongation, approximately constant stress conditions were maintained by systematically reducing the load manually. RESULTS As part of an investigation of the superplastic properties of the eutectic Zn-A1 alloy, evidence was obtained for the development of elliptically shaped cross sections as originally round specimens were extended. For example, after an elongation of about 100 pct, a round specimen with an initial diameter of 0.150 in. became elliptical with major and minor axis of 0.128 and 0.88 in., respectively. Photographs are presented to illustrate the ellipticity developed during superplastic deformation, Fig. 1. The specimen shown was deformed at a stress of 500 psi, at a temperature of 285°C, and a strain rate of 2.28 x 10-2 min-1. The strain-rate sensitivity exponent* was measured at *The strain-rate sensitivity exponent, m, is defined as d In o/d In c where o is the steady-state flow stress and E is the strain rate. this temperature and in the strain rate range 10"3 to 10-1 min-1 was found to be about 0.5. This value is typical of those observed with superplastic materials. The material studied exhibited negligible strain hardening during superplastic deformation, the creep rate remaining constant under constant stress and temper-

Jan 1, 1969

By H. Siebel, N. A. D. Parlee

MIZIKAR, Grace, and parlee' studied rates of absorption of oxygen in stagnant liquid silver in a new type of open-ended gas-liquid metal diffusion cell, where the capillary diameters used were 1.5, 2, and 3 mm. They reported that the rates appeared to be controlled by the rate of diffusion of oxygen atoms in liquid silver and they used their data to arrive at the following equation as a reasonably good representation of the diffusivity (D) of oxygen in liquid silver: D = (14.7)10-4 exp (-7100 ± 3200)/RT cm2/sec Since this type of diffusion cell offers a promising method of measuring diffusivities of gas atoms in liquid metals, the senior author of this note and his students are carrying on a critical examination of the method, and are attempting to improve and extend the technique. The research reported briefly here was designed to examine more carefully the earlier conclusion1 that the absorption rate is diffusion-controlled, and to find out whether the diameter of the cell could be greatly increased and thus extend the method to systems where gas solubilities and diffusion rates are much smaller than in the case of oxygen in silver. For the purpose of these experiments, the open-ended capillary cell used by Mizikar, Grace, and Parlee was replaced by a small cylindrical crucible (1 to 1.7 cm in diam) containing pure silver (to a depth of 1.3 to 3 cm) resting in the bottom of a closed-ended vertical quartz tube, with an evacuated quartz filler tube just above the crucible to reduce dead volume. The method of measuring the rate of absorption was otherwise very similar to that of Mizikar, Grace, and Parlee and all the same precautions were taken. A much smaller and shorter tube furnace was used for heating, but simi- lar precautions about temperature gradients were observed. This technique was nothing more than the application of a Sieverts apparatus to the measurement of rates of absorption in small crucibles of stagnant liquid silver. In each run the volume of gas absorbed (V) was plotted against the square root of time (vt) and apparent diffusivities were calculated from the slope of the line, as described by Mizikar, Grace, and parlee.' Care was taken to use only the data obtained during the early part of the total absorption period while the cell functioned as one of infinite depth. The results at 1000°C are summarized in Table I and Fig. 1. The following conclusions may be drawn: 1) Diffusion cells up to 1.7 cm in diam yield, within experimental error, the same values for the diffusivity of oxygen (D) as the capillary cells of 1.5, 2, and 3 mm in diam employed by Mizikar, Grace, and Parlee. Cell diameters as large as 1.7 cm are probably not desirable for the most precise work. Intermediate sizes, perhaps 0.5 cm, will be most practical. 2) All absorptions measured were consistent with a model where the rate is controlled by the diffusion of gas atoms in the metal. The fact that runs at absorption pressures ranging from 0.1 to 1 atm (at any one temperature) give

Jan 1, 1965

By J. L. Zakin, G. K. Patterson, J. M. Rodriguez

Correlation has been obtained between drag-reducing characteristics for turbulent flow in a pipe and measurable properties of several polymer solutions. Several concentrations of high molecular weight polymethyl methacrylate in toluene, high molecular weight polyisobutylene in both toluene and cyclohexane, medium molecular weight polyisobutylene in cyclohexane and benzene and low molecular weight polystyrene in toluene were studied. Data obtained in these nonpolar solvents and literature data for more polar solvents were successfully correlated as the ratio of measured friction factor to purely viscous friction factor vs the modified Deborah number vrl/D0.2 where 71 is the first-mode relaxation time of the solution estimated by the Zimm theory. A shift factor which is a function of intrinsic viscosity 1/(4[?] - 1) allowed all the data obtained with nonpolar solvents to be correlated as a single function. For these systems, most of the data fit a single curve to within + 5 percent of the average friction factor ratio. The shift factor did not give a unique function of the data for the more polar systems. INTRODUCTION The phenomenon of drag reduction in polymer solutions was first studied by Toms1 in dilute solutions of polymethyl methacrylate in mono-chlorobenzene. The drag ratio for flow through circular tubes has been defined2 as the ratio of the pressure. drop of the solution to the pressure drop of the solvent at the same flow rate. The drag ratio is less than 1.0 for a drag-reducing fluid. Practical use of drag reduction is being made in fracturing operations in the petroleum industry.3 A more fundamental quantity is the friction factor ratio, defined as the ratio of the observed pressure drop to that predicted for a solution of the same viscosity characteristics and density at equal flow rates using the Dodge-Metzner friction factor equation4 Viscous solutions with drag ratios greater than 1.0 can have friction factor ratios less than 1.0. For practical applications, it is drag reduction which is of interest. However, for correlation the fundamental ratio is the friction factor ratio. In recent years, drag reduction has been studied extensively. Recent studies have shown that reasonable predictions of the incipience of drag reduction in polymer solutions can be made from the properties of the solutions and the flow Variables.5 However, it has not been possible to predict accurately the amount of drag reduction to be expected for a given polymer solution without any drag-reducing turbulent flow data on the same solution.6 For flow through circular tubes it is well established that there is a concentration effect and a diameter effect on drag reduction. Toms1 observed that drag reduction increases with an increase in the concentration of the solution up to an optimum concentration beyond which, due to the increased viscosity of the solutions, the drag ratio increased with an increase in concentration. Hershey 7 observed that for dilute Newtonian polymer solutions in nonpolar hydrocarbon solvents, a normal transition region may be obtained followed by a departure from the von Karman equation (on a friction factor-generalized Reynolds number chart). The point of departure is a function of diameter: the smaller tubes depart at the lower Reynolds numbers. Concentrated solutions may show no abrupt transition region, but merely an

By M. W. Legatski, D. L. Katz

The best currently available description of the longitudinal mixing properties of a porous medium is an equation of the form which relates the effective longitudinal dispersion coefficient Dp to the molecular diffusion coefficient Do, the electrical resistivity factor F, the porosity <f> and a Peclet number. If the parameters dpa and m are determined for a porous medium of known porosity and electrical resistivity factor, then a dispersion coefficient may be estimated for a given flow rate and a given gas pair. A new method, featuring on-line gas analysis by thermal conductivity and on-line data reduction by analog computation, was developed and used to determine these mixing parameters for eight naturally occurring sandstones and two dolomite samples. The exponent m of the above equation was found to vary between 1.0 and 1.5. The characteristic length dpa in the above equation was found to vary between 0.25 and 1.9 cm, with an average value of 0.4 cm for sandstones. Measurements were made on two cores in which paraffin wax had been deposited by evaporation from a pentane solution. They indicated that the presence of an immobile phase such as connate water could increase the dispersion coefficients significantly. INTRODUCTION While the petroleum and chemical industries have studied the mixing of miscible liquids flowing in consolidated porous media and of miscible gases flowing in unconsolidated porous media, relatively little data have been presented to describe the mixing of gases flowing through consolidated porous media. Such data are of particular interest to the gas storage industry. For instance, the U. S. Bureau of Mines is storing large quantities of a rich helium-nitrogen gas in contact with a natural gas in a dolomite reservoir. Since the rich gas occupies only 15 percent of the total reservoir volume, it is essential that the extent of rich gas-natural gas mixing be predicted and understood as a function of rock properties, pressure and rate of movement. This investigation was concerned only with the determination of longitudinal dispersion coefficients. It is understood that a transverse dispersion coefficient, which characterizes mixing perpendicular to the direction of flow, may be an order of magnitude less than the coefficient characterizing mixing in the direction of bulk flow.5719 It should also be recognized that the use of any dispersion coefficient is in itself a simplification. It is necessary to assume that mixing in a porous medium may be characterized by the equation for flow in a single direction. A number of authors1 l8,19 have pursued the mixing problem, not in terms of the so-called "dispersion model" described by Eq. 1, but in terms of a "mixing cell model". This model supposes that a porous medium is constructed of a large number of small mixing chambers and that the concentration of the diffusing component within each mixing chamber is uniform. Fick&apos;s law (Eq. 1) assumes that there is no gross by-passing of one fluid by another, and that there are not stagnant pockets of gas in the system under consideration as discussed by Coats and Smith.8 These assumptions are not always valid for flow through porous media and it is important to recognize the limitations upon Eq. 1. The most serious limitation upon the assumption of Fick&apos;s law mixing in a porous medium is

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts&apos; method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts&apos; method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts&apos; law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts&apos; law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts&apos; law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts&apos; law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult&apos;s law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and&apos; oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1&apos;2 The PbO-SiO2 melts are ionic conductors.&apos; During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By J. W. Spretnak, G. W. King

THE crystallography and morphology of 0-Al,Fe precipitates in an A1 + 0.5 wt pct Fe alloy have been studied by transmission electron microscopy. The alloy was cast in cylindrical ingots, 15 cm in diameter and 60 cm in length, and cooled slowly. The measured composition was 0.527 wt pct Fe, 0.001 wt pct Mg, and 0.003 wt pct Cu. Spectrographic analysis revealed no additional trace impurities. Thin slices were cut from the ingot and reduced by more than 95 pct by rolling to a thickness of 0.1 mm with no intermediate annealing treatments. These thin sheets were then vacuum-annealed for 1 hr at 612°C and air-cooled in their capsules. Thin foils for examination in the electron microscope were prepared by electropolishing. The precipitate is found in the form of oval platelets on the (110) planes of the matrix. The major axes of the platelets are parallel to the (110) directions of the matrix, and vary in length from 1/2 to 2 p. The thickness is about 1/10 p. Examples of platelets, both in the plane of the foil and normal to the foil, are shown in Figs. l(a) and l(b), respectively. lack&apos; found that ?-A13Fe (more correctly All13Fe4) belongs to the monoclinic system. Using Black&apos;s structural data and simultaneous electron-diffraction patterns from the matrix and precipitates, the habit planes and directions were determined to be: (00l)? || (110)Al [100]? || [001]Al The orthogonal crystallographic axes of the precipitates are accurately in the habit plane, while the measured coincidences of the directions are only within 10 deg. The major axis of the platelet is parallel to [010] in the 0. This orientation corresponds to the direction of nearest registry of the lattices.

Jan 1, 1964

By K. D. Jacob, H. L. Marshall, D. S. Reynolds

All types of commercial phosphate rock produced throughout the world contain fluorine in quantities ranging from approximately 0.4 to 1.3 per cent in the Curacao and Christmas Island phosphates to 3.1 to 4.2 per cent in the phosphates of the United States and North Africa1. For a given type of rock, the fluorine content is usually roughly proportional to the phosphorus content. Significance of Fluorine in Phosphate Rock On the basis of chemical and X-ray diffraction studies, Hendricks and co-workers2 concluded that fluorapatite, Cal10F2(PO4)6, is the essential phosphatic constituent of the commercial types of domestic phosphate rock. On the other hand, Bredig and co-workers3 have recently advanced the opinion, also based on X-ray diffraction studies, that the mineral phosphates usually contain carbon dioxide in the apatite lattice, and that the phosphate rocks of the United States are really fluorcarbonate apatites. However, the domestic types of phosphate rock do not seem to differ greatly from coarsely crystalline fluorapatite in their behavior toward chemical reagents in general, and for the purpose of this paper it will suffice to consider fluorapatite as being the essential phosphatic constituent of these types of rock. The available data1 indicate that the different commercial types of domestic phosphate rock usually contain about 12 to 52 per cent more fluorine than theoretically is required to form fluorapatite with all the phosphorus. Calcium fluoride (fluorite) has been definitely identified in only a very few of the samples that have been examined1,2. Bredig and co-workers4 state that fluorapatite can take into its crystal lattice excess calcium fluoride to the extent of approximately 70 per cent of that theoretically required by the formula Ca10F²(PO4)6 without causing more

Jan 1, 1938