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By Amitava Gangulee, Michael B. Bever

The order-disorder transition in Ag-Mg alloys in the range 17 to 26 at. pct Mg was investigated and some thermodynamic, electrical and mechanical properties of ordered Ag-Mg alloys were measured. A modification of the phase diagram is proposed on the basis of measured transition temperatures. The stability of the ordered structure is analyzed in terms of the quasichemical theory. Kinetic aspects of the order-disorder transition were also investigated. The energies of ordering at 273°K of Ag-Mg alloys were measured by liquid metal solution calorimetry. The electrical resistivities and the tensile Properties of the ordered alloys were measured. The exothermic energy of ordering increased with magnesium concentration up to the composition Ag3Mg; it is discussed in terms of the quasichemical theory. Pronounced order hardening was observed and can be explained by several strengthening mechanisms, which are particularly effective because of a change in crystal structure associated with the ordering transition. IN silver-rich solid solutions containing approximately 17 to 26 at. pct Mg, long- range ordering may occur during appropriate therma1 treatments. Clare-brough and Nicholas1 first detected such long-range order in the solid solution of composition Ag3Mg and suggested that the unit cell of the superlattice contained 256 atoms. x-ray2 and electron diffraction3 investigations confirmed the occurrence of long-range order, but indicated a shifted Ll2-type structure. On the basis of recent X-ray measurements the crystal structure of ordered Ag3Mg has been confirmed as type D023.4 The present paper is concerned with the order-disorder transition in silver-rich Ag-Mg solid solutions and some thermodynamic, electrical, and mechanical properties of the ordered alloys. The effects of short-range order on the properties of silver-rich solid solutions containing up to 26 at. pct Mg are discussed in a concurrent paper.5 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Specimens of Ag-Mg alloys containing from 18 to 26 at. pct Mg were prepared in the form of 1.0-mm-diam wires as described in Section 1.1 of Ref. 5. Disordered specimens were prepared by annealing at 773°K for 1 hr and quenching into iced brine. Ordered specimens were prepared by annealing at 773°K for 1 hr and slowly cooling to room temperature over a period of 15 days. The specimens were stored at 78°K. 1.2) Resistivity Measurements. Electrical resistivi- ties were measured by a potentiometric method.' Equilibrium values were obtained at several temperatures. The kinetics of ordering were investigated by following the time-dependent changes of the resistivity of initially disordered specimens during annealing. The specimens were enclosed in copper capsules and immersed in salt pots; the heating up was accelerated by injecting preheated helium into the capsules. 1.3) Calorimetry. The energies of ordering of the alloys were measured in a tin solution calorimeter as the difference between the heat effects of additions of completely ordered and disordered specimens of the same composition. The procedure and the method of calculation have been described.6 Magnesium was used for thermal compensation in most calorimetric runs in order to improve the accuracy.677 1.4) Mechanical Tests. Tensile tests were carried out with wire specimens at room temperature as described in Section 1.5 of Ref. 5. Microhardness measurements were also made.? 2) RESULTS AND DISCUSSION The characteristics of the order-disorder transition of silver-rich Ag-Mg solid solutions will be discussed first. Some thermodynamic, electrical, and mechanical properties of the ordered alloys will then be considered and compared with the corresponding properties of dis-disordered alloys. 2.1) The Order-Disorder Transition. 2.1.1) Thermodynamic and Structural Aspects. The transition temperatures Tt were determined from discontinuities in the slope of the equilibrium resistivity vs temperature curves. Normalized curves for three compositions are shown in Fig. 1. The transition temperature increases with the magnesium concentration and reaches a maximum at the stoichiometric composition Ag3Mg. The transition temperature of the alloy Ag3Mg was measured as 665° ± 2°K and compares with published values of 660°,1 663°,8 and 66°k.3 In the slopes of the resistivity vs temperature curves of alloys containing 22.2 and 22.5 at. pct Mg, discontinuities were observed at two temperatures. Such upper and lower discontinuities indicate a two-phase field. A modified form of the published phase diagram9 is shown in Fig. 2. A two-phase field was found only on the low-magnesium side of the composition Ag3Mg. On the high-magnesium side, the existence of a two-phase field could not be established because of insufficient resolution, but such a field must be present. This part of the phase diagram can be made complete by a eutec-toid-type reaction a = (a' + ß). The existence of a boundary between the two-phase fields (a + ß) and (a' + ß) is also in accord with published lattice parameters.3 The crystal structure of ordered Ag3Mg (type Do23)

Jan 1, 1969

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish, or animal life in field tests or in controlled experiments.

Jan 1, 1950

By I. W. L. Finlay, H. R. Ogden, R. Jaffee, D. J. Maykuth

Aluminum has been found to be soluble in a titanium to about 26 pct, and to raise the temperature range of transformation from a to 8. Two intermediate phoses exist in the system, a new face-centered tetragonal phase, designated as 7, which occurs between 34 and 46 pct Al, and TiAI Metallographic and X-ray diffraction data were used to determine the diagram. ALUMINUM is one of the useful alloying additions for titanium-base alloys. It is an important constituent in two commercial alloys released in 1950, one containing 4 pct A1 and 4 pct Mn, and the other containing 3 pct A1 and 5 pct Cr as the metallic alloy content. It is probable that, in the future, other titanium alloys containing aluminum will be released. In the course of alloy development work, some of the features of the constitution of titanium-rich Ti-A1 alloys have been developed. These are described in the present paper. The only available information on the Ti-A1 system concerns the aluminum-rich end of the diagram. In summarizing the early work, Hansen' indicated that there is little solubility of titanium in aluminum, and that a two-phase region exists up to the intermediate compound, TiA1a (37.2 wt pct Ti), which has a congruent melting point at 1355°C. Fink' has reported that a peritectic reaction occurs at 665°C between the melt and TiA1³ to form the terminal solid solution of titanium in aluminum. The solubility of titanium in aluminum has been established at 0.24 pct at 510°C and is estimated to be between 1 and 1.5 pct at the peritectic temperature. No information has been published on the diagram above TiAl,, other than a statement- hat aluminum raises the a to ß transformation temperature of titanium. Materials and Preparation of Alloys Iodide-type titanium and high-purity aluminum were used in this investigation. Typical analyses of these materials are given in Table 1. Alloys were prepared by arc melting on a water-cooled copper hearth, using the techniques described previously for contamination-free melting.' Weight losses during melting were very low, ranging from 0 to 0.02 g in a 10 to 15 g charge, indicating that little or no loss of aluminum occurred during melting. This permitted the use of nominal compositions for these alloys. Alloy ingots containing from 0 to 7.5 pct A1 were rolled in air at 850°C to 0.040 in. sheet. Alloys containing from 7.5 to 16 pct A1 could only be rolled about 25 pct reduction at temperatures up to and including 1200°C. Alloys containing above 16 pct A1

Jan 1, 1952

By H. M. Wilten

THIS article presets a view of a problem encountered in petroleum refining in the deterioration of equipment used in condensation of vapors and cooling of liquids. Discussion is limited to the problems of shell- and tube-type exchangers and condensers. In this service shell- and .tube-type equipment is gradually displacing other types and, for this reason, its economic importance ill oil-refining practice is also increasing. Considering oil - refinery practice during the last two decades one can readily see many important improvements in the apparatus used. Briefly, the present equipment is safer, more efficient, and Ignore economical. Improvement in apparatus used for the condensation of distillates has, in my opinion, been less than that in other essential distilling apparatus. So it is hoped that this discussion will stimulate research among the producers as well as among the consumers of this equipment with a view to ameliorating this condition.

Jan 1, 1937

By L. S. Darken

IN the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be repre-sented satisfactorily by the simple equilibrium expression K - (p1)p1 (p2)p2 . (R1)r1(R2)r2 . where (P) denotes the concentration of a product and (R) the concentra-tion of a reactant in the reaction r1R1 + r2R2 + . . . Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a com-ponent is not proportional to its true mol fraction, But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple com-ponents and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satis-factorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature as ionization or the occurrence of polar and nonpolar molecules-are presumably less effective in metal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By T. J. Woodside

A. E. LEE*—One question of the flue leading to the tube coolers. What gas velocity is maintained to prevent settling of the finely divided fume ? T. J. WOODSIDE (author's reply)— 30 fps. Of course some fume settles out, but is immediately carried away by the screw conveyors. H. R. BIANCO —How effective are the soot blowers ? Do you have to use any hand lancing? T. J. WOODSIDE Only one point, which is right at the top of the economizer and which the soot blowers do not reach, we occasionally hand lance. But everywhere else the soot blowers have been very effective and no hand lancing has been done. L. V. DAVIDSON*—Do you have considerable variation in the lead content of the fume collected if the lead is higher, and is there greater tendency for the fume to stick on the boiler tubes ? T. J. WOODSIDE—There is very little variation in the lead content. From 5 to 7 pct is the widest range variation we have had and we have noticed no difference in the behavior of the fume. C. R. KUZELL—Mr. Woodside has been quite generous with data pertaining to metal and fuel economics. I think he stated that the coal consumption of the furnace was 21/10 21/10 for a pound of zinc recovered. I take it that that is the gross coal input to the furnace. I wonder what the net fuel consumption in terms of coal might be after crediting the fuel equivalent of the waste heat steam recovered? T. J. WOODSIDE—The fuel value of the waste heat steam is approximately 42 pct of the heat input to the furnace. A very large part of the heat, of course, goes out in jacket water—44 pct. A. D. TERRELL*—I would like to know how much lead is in the deleaded material. T. J. WOODSIDE—It is a little less than 2 pct now.

Jan 1, 1950

By E. H. Greener, M. E. Fine

The internal friction (1/Q) of cobalt Fig. 1 (measured by an electrostatic dynamic method1) near 250°C begins to increase rapidly on heating and continues to increase until 560°C, the highest tem- perature measured. In the plot of log of 1/Q against 1/T, above 250°C the data nearly fit two straight lines intersecting at 400°C, approximately the temperature of the hexagonal-cubic transformation. The higher temperature branch corresponds to an effective activation energy of 6500 cal per mole, the lower temperature branch 11,000 cal per mole. Young's modulus Fig. 2 increases approximately

Jan 1, 1959

By K. S. Milliken

NORMAN W. Lord&apos; has shown that the resultant impurity distribution after n zone passes is given by in the ingot section OSa<N—n, where a is the displacement in zone lengths, N is the ingot length in zone lengths, C,, is the initial uniform impurity concentration, k is the segregation constant = Ceoll C,,,,,,,, at equilibrium, and The foregoing expression is formidable in respect to computational labor. However, the triple sum can be reduced as follows is better if computing for only a single value of n. For k<l, it can be shown that this last equation is equivalent to The infinite series is useful only when k is small enough to force rapid convergence. In such cases, the absence of subtraction from unity has the definite advantage of preserving accuracy. Acknowledgments It is a pleasure to acknowledge stimulating correspondence with Dr. Howard Reiss of Bell Telephone Laboratories Inc. This note is published by permis-sion of the Deputy Minister, Dept. of Mines and Technical Surveys, Ottawa, Ont., Canada.

Jan 1, 1956

By Alexander Field

IN THE light of the experimental data on equilibrium for the reaction C + FeO = Fe + CO in molten steel recently obtained by Kinzel and I Egan,1 it is necessary to revise current theories regarding the nature of equilibrium between carbon and FeO in the basic open-hearth furnace. According to the measurements of these investigators the equilibrium constant m for the above reaction for a pressure of dissolved CO equal to 1 atm. is equal to 0.0005 at 1550° C., when concentrations of carbon and. FeO are expressed in percentages by weight. Their work also shows that, with the pressure of CO fixed at 1 atm., not only is the product of carbon and FeO constant, but carbon and FeO are each independently constant-a circumstance which might have been predicted from theoretical considerations. At 1550° C., carbon is constant at about 0.025 per cent. and FeO at about 0.020 per cent., with the pressure of dissolved -CO equal to 1 atm., the product of these two constants being equal to the originally mentioned constant of 0.0005. Available data on the dissolved FeO content of samples taken from the metal bath at practical slag-metal equilibrium prove that this FeO content is determined solely by temperature and the effective FeO content of the slag. The distribution constant r at 1550° C., as determined by Herty, Gaines, Larsen, Simkins, Geruso and Watkins2 is equal to 0.0086. A slag would have to contain 0.020/0.0086 = 2.3 per cent. effective FeO or less in order to prevent the metal from containing more dissolved FeO than that required for equilibrium with CO at 1 atm. pressure. Such low percentages of FeO are never found in basic open-hearth slags at the completion of a heat when rate of carbon drop has become practi-

Jan 1, 1930

By W. G. Pfann

In zone-melting, a small molten zone or zones traverse a long charge of alloy or impure metal. Consequences of this manner of freezing are examined with impurerespect to solute distribution in the ingot, with particular reference to purification and to prevention of segregation. Results are expressed in terms of the number, size, and direction of travel of the zones, the initial intermsofsolute distribution, and the distribution coefficient. IF a charge of binary solid-solution alloy is melted and then frozen slowly from one end, as for example in the Bridgman method of making single crystals,&apos; coring usually occurs, with a resulting end-to-end variation in concentration. Such coring, or normal segregation, is undesirable where uniformity is an object. On the other hand, for certain systems, it can be utilized to refine a material by concentrating impurities at one end of the ingot.&apos;. &apos; In the present paper a different manner of freezing will be examined with respect to the distribution of solute in the ingot. A number of procedures will be indicated which have in common the traversal of a relatively long charge of solid alloy by a small molten zone. Such methods will be denoted by the general term zone-,melting, while the process described in the preceding paragraph will be called normal freezing. It will be shown that, in contrast to normal freezing, zone-melting affords wide latitude in possible distributions of solute. Segregation can either be almost entirely eliminated or it can be enhanced so as to provide a high degree of sttparation of solute and solvent. A number of simplifying assumptions will be invoked which, while not entirely realizable in practice, nevertheless provide a suitable point of departure for more refined treatments. Moreover, our own experience with zone-melting has shown that, for certain systems at least, the analysis holds quite well. The present paper will be confined to a discussion of principles and a general description of procedures. Comparison with experiment is planned for later publication. Normal Freezing Before considering zone-melting, segregation during normal freezing will be reviewed briefly. If a cylinder of molten binary alloy is made to freeze from one end as in Fig. 1, there usually will be a segregating action which will concentrate the solute in one or the other end of the ingot. If the constitutional diagram for the system is like that of Fig. 2, then the distribution coefficient k, defined as the ratio of the concentration in the solid to that in the liquid at equilibrium, will be less than one and the solute will be concentrated in the last regions to freeze. If the solute raises the freezing point, then k will be greater than one and the solute will be concentrated in the first regions to freeze. The concentration in the solid as a function of g, the fraction which has solidified, can be expressed by the relation: C = kC0 (1-g)k-1 [I] where C, is the initial solute concentration in the melt. Eq 1 is based on the following assumptions: 1—Diffusion in the solid is negligible. 2—Diffusion in the liquid is complete (i.e., concentration in the liquid is uniform). 3—k is constant. Concentration curves representing eq 1 for k&apos;s from 0.01 to 5.0 are plotted in Fig. 3. This equation, in one form or another, has been treated by Gulliver,³ Scheuer,4 Hayes and Chipman5 for alloys and by McFee2 for NaCl crystals. It is derived in Appendix I. It should be pointed out that the k which is calculated from the phase diagram will be valid only in the ideal case for which the stated assumptions are correct. In all actual cases, the effective k will be larger than this value for solutes which lower the melting point, smaller for solutes which raise the melting point, and will probably vary during the beginning of the freezing process. For simplification it will be assumed that the ideal k is valid. Zone-Leveling Processes The processes of this part are designed to produce a uniform, or level, distribution of solute in the ingot. Single Pass: Consider a rod or charge of alloy whose cross-section is constant and whose composition, C2, is constant, although permissibly varying on a microscopic scale." Such a charge might be a rapidly frozen casting or a mixture of crushed or powdered constituents. Cause a molten zone of

Jan 1, 1953

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.&apos; 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 R. H. Gautschi, F. C. Langenberg

Rare-earth additions were made to laboratory heats of Type 310 stainless to observe their effect on as-cast ingot structure, nitrogen and sulfur contents, and nonmetallic inclusions. Lanthanum had a grain-refining effect in 30-lb ingots, but results with 200-lb ingots were inconsistent. Cerium, lanthanum, and misch metal lowered the sulfur content when the sulfur exceeded 0.015 pct and the rare-earth addition was greater than 0.1 pct. The rare-eardh content in the metal dropped very rapidly within the first few minutes after the addition. The size, shape, and distribution of nonmetallic inclusions was not changed in 30-lb ingots, but changes were noticed in larger ingots. RARE-earth* additions have been made to austenitic Cr-Ni and Cr-Mn steels to improve their hot workability. The high alloy content of these steels often results in a considerable resistance to deformation and inherent hot shortness at rolling temperatures, particularly in larger ingots. Rare earths in the metallic, oxide, or halide form are usually added to the steel in the ladle after deoxidation although they can be added in the furnace prior to tap or in the molds during teeming. The literature- indicates that the effects of rare-earth treatments on these stainless steels are not consistent, and sometimes even contradictory. Since no mechanism has been presented which satisfactorily accounts for the claimed improvements, the effects of rare earths are a qualitative matter. The work described in this paper was initiated to expand the knowledge of the effects of rare-earth additions on melting variables such as ingot structure, chemical analysis, and nonmetallic inclusions. REVIEW OF LITERATURE Ingot Structure—Rare-earth additions to stainless steels have been reported to cause a change in primary ingot structure in that there are fewer coarse columnar grains. However, the results are inconsistent. While one investigation1 has shown a large reduction in coarse columnar crystals, another2 has been unable to observe this effect, particularly when small ingots were poured. Post and coworkers3 observed ingot structures for a number of years and found that the columnar type of structure is not definitely a cause of any particular trouble in rolling or hammering, provided the alloy is ductile. Knapp and Bolkcom4 found rare-earth additions to be quite effective in preventing grain coarsening in Type 310 stainless steel. Chemical Analysis—Many effects of rare-earth treatment on chemical analysis have been claimed in the literature. Russell5 observed that some sulfur is removed by rare-earth metals, and that a high initial sulfur content improved the efficiency of sulfur removal. Lillieqvist and Mickelson6 report that rare-earth treatment causes sulfur removal in basic open-hearth furnaces, but not in basic lined induction furnaces. Knapp and Bolkcom found no sulfur removal in acid open-hearth and acid electric furnaces, probably because the acid slag can not retain sul-fides. snellmann7 showed that sulfur could be lowered apprecfably with rare-earth additions; however, a sulfur reversion occurred with time. Langenberg and chipman8 studied the reaction CeS(s) = Ce(in Fe) + S(in Fe), and found the solubilit product [%Ce] [%S] equal to (1.5 + 0.5) X 10-3&apos;at 1600°C. Results in 17 Cr-9 Ni stainless were about the same as those in iron. Beaver2 treated chromium-nickel steels with 0.3 pct misch metal and observed some reduction in the oxygen content. He also noted an inconsistent but beneficial effect of rare earths when tramp elements were present in amounts sufficient to cause difficulty in hot working. It is not known whether rare earths reduce the content of the tramp elements or change the form in which these elements appear in the final structure. No quantitative data are available concerning a possible effect of rare-earth treatment on hydrogen and nitrogen contents. However, Schwartzbart and sheehan9 stated that additions of rare earths had no effect on impact properties when the nitrogen content was low (0.006 pct), but served to counteract the adverse effects of high nitrogen content (0.030 pct) on these properties. Knapp and Bolkcom4 analyzed open-hearth heats in the treated and untreated conditions and found the nitrogen content (0.006 pct) to be unaffected. These two results lead to the speculation that rare-earth additions can reduce the nitrogen content to a certain level. Decker and coworkers10 have observed that small amounts of boron or zirconium, picked up from magnesia or zirconia crucibles, increased high-tem-

Jan 1, 1961

By J. H. Wernick

IN a study of the rate of decomposition of %-in. cubes of limestone, dolomitic limestone, and dolomite in a sweeping nitrogen atmosphere, Joseph, Beatty, and Bitsianes&apos; found that the zone of calcination advanced at substantially a constant rate at a given temperature. The purpose of this paper is to show that their data indicate at least two processes occurring when the above carbonates decompose. It is suggested that there are two processes occurring consecutively, one the limiting process in a given temperature range and the other the limiting process over another temperature range. The data of Joseph and co-workers have been extended by use of the Arrhenius equation, Eq. 1, a relation beween the velocity constant k of a reaction and the absolute temperature T. d In k A &apos; dT Rr2 A is the activation energy in calories per mol (additional energy that must be added for an average molecule to react), and R is equal to 1.986 cal

Jan 1, 1955

By F. R. Brotzen, J. Taranto

SEVERAL investigators have computed stacking-fault concentrations from X-ray diffraction data.&apos;-&apos; The method generally employed relates the line shift to the stacking-fault probability. In this investigation platinum filings of 99.99 pct purity screened to -325 mesh were studied after having been subjected to various annealing treatments. The lines were measured on a General Electric XRD-5 spectrogoniometer using CuK, radiation. The centroid of the broad reflections was determined by the method proposed by pike.&apos; The stacking-fault probability was calculated by the formula given by Warren and warekois,3 with the assumption that all stacking faults were on the (111). Various high-angle reflections were used, but most data collected refer to the shift in the (400) reflections. When the filed platinum powder was annealed at 1200°C for 20 min the stacking fault concentration was too small to be detected. The stacking-fault probability in freshly filed specimens, as determined by the line shift relative to the annealed specimen, was about 0.016, Fig. 1. If the faults would be created only by extended dislocations, the dislocation density in the filed specimen would be about 3X1012 cm-2. The average stacking-fault width of about 21 which was used in this computation, is that given by Thornton and Hirsch.7 The mechanism by which stacking faults are annihilated during annealing is not yet fully understood. The isothermal results obtained do not seem to support the simple hypothesis of a first-order decay. On the other hand, the analysis by Kuhlmann, Masing, and Raffelsieper8 for the loss of dislocations during recovery agrees much better with the experimental data of this investigation. This analysis yields an activation energy of 29 ± 8 kcal per mol for the disappearance of stacking faults in cold-worked platinum during annealing. Even if one takes into account the lack of accuracy inherent in this X-ray method, the activation energy found is substantially less than that of self-diffusion in platinum, i.e., 61.6 kcal per mol.9 The results therefore suggest that processes other than dislocation climb, which involves the activation energy of self-diffusion, are responsible for the loss of stacking faults in platinum during annealing. The broad reflection lines became sharper early in the recovery process, Fig. 1. The sharpening occurred well before the stage during which stacking faults disappear. This lends support to Nowick&apos;s10

Jan 1, 1962

MONTANA SECTION W. C. SIDERFIN, Chairman, OSCAR ROHN, Vice-Chairman, E. B. YOUNG, Secretary-Treasurer, 526, Hennesey Building, Butte, Mont. F. W. BACORN, C. D. DEMOND. The semi-annual meeting of the Montana Section was held at the Silver Bow Club, Butte, Montana, on Friday, Nov. 16, at 8 p. m.; this was a postponement of the regular October meeting because of conflict in date with the St. Louis meeting of the Institute. An informal dinner was served to 68 members and guests. After dinner, Chairman W. C. Siderfin called the meeting to order. The minutes of the annual meeting, of Feb. 2, 1917, and the special meeting of May 21, 1917, were read and approved. C. W. Goodale led the discussion with "Notes on the St. Louis Meeting." He was followed by J. H. Warner who spoke on " The Joplin and Miami Districts," and by J. L: Bruce, Alexander Leggatt, N. B. Braly, and E. B. Young, the latter speaking on the work of the War Minerals Committee; and on the Cosden Oil Refinery at West Tuba, Okla. R. H. Sales reviewed briefly the manganese situation. E. N. Norris presented a paper on "Fire Proofing of Mine Shafts by the Anaconda Copper Mining Co." This resulted in interesting discussion by C. L. Berrien, C. E. Nighman, N. B. Braly, W. B. Daly, B. H. Dunshee, and J. J. Carrigan. C. L. Berrien and C. E. Nighman presented their papers on "Fire Extinction by Hydraulic Filling." In view of the late hour, discussion was waived. The executive committee, by unanimous consent, decided to request written discussion of the above papers to be presented at the next meeting, in February. B. B. Thayer spoke interestingly on the work of the Naval Consulting Board, and referred to the arsenic situation. Spencer Miller, also a, member of the Naval Consulting Board, entertained the-meeting with a vivid description of the method of "Coaling Battleships at Sea." Robert Sticht of Tasmania, in a short talk, spoke feelingly of his relations with the United States. At a late hour adjournment ended a most successful and interesting meeting. E. B. YOUNG, Secretary.

Jan 1, 1918

By H. C. Burghard, F. R. Brotzen

Experiments were performed to determine the effects of mechanical vibrations on ordering in CuAu. The effects of 5, 10, and 15 kc vibrations were investigated over a range of ordering temperatures of 280° to 360°C. A decrease in the rate of ordering was observed at all frequencies and ordering temperatures. THE effects of mechanical vibrations on certain solid-state reactions have been noted by several investigators. In 1930, Mahoux&apos; reported a substantial increase in the case depth of a steel sample nitrided under the influence of mechanical vibrations over that of an unvibrated sample. Similarly, an accelerating effect of vibrations on the diffusion of chromium in steel was noted. Guillet, in the same year, confirmed the results of Mahoux. More recently Schenck and schmidtmann3 studied the effects of low-frequency, alternating loads on the diffusion of carbon in steel. The results of their experiments, conducted at 500 cycles per min and large strain, (0.2 pct), indicated an acceleration of the process. These workers also reported an increase in case depth of a sample vibrated at 430 kc during a carburizing treatment. Effects of high-frequency vibrations on solid-state reactions have also been investigated by Gudzoff and Gavze6 and Fairbanks and Dewez.7 The former reported an acceleration of the age-hardening process in aluminum alloys. The latter noted changes in the structure and mechanical properties of steel annealed under the influence of vibrations. On the other hand, Altenburg4 and Ehringer5 have given some theoretical reasons and experimental evidence as to the improbability of any effect of vibrations on diffusion. Comprehensive surveys of the effects of vibrations on metallurgical reactions are given by Hiedemann&apos; and Bergmann.9 None of the above investigations led to a physical description of the effects of mechanical vibrations on solid-state reactions. In the present study an attempt was made to gain an understanding of the influence of vibrations on nucleation and diffusion. The order-disorder transformation was chosen for investigation since its mechanism has been extensively discussed in the literature. Moreover, the progress of the transformation may be easily followed by observation of electrical resistance changes. EXPERIMENTAL PROCEDURE The specimens used for the experimental observation of ordering rates were prepared from 50 at. pct Cu-Au alloy wire.* Each specimen consisted of a 0.02-in. diam wire approximately 10 in. long to which two copper potential leads were silver soldered, 2 1/2 in. apart, near one end of the wire. A 1/8-in. diam by 1/4-in. long steel stub was silver soldered

Jan 1, 1960

By Willard P. Ward

SOME TIME in the year 1874 or 1875, I conceived the idea that spiegeleisen might be made -in a blast furnace from ores that were not carbonates, and which did not contain both manganese and iron in the same ore. Up to this time, such ores had formed the basis of all the spiegel that had been produced; and all the ferromanganese that was on the market before 1875 was made in crucibles, and cost about 00 per ton, for 80 per cent. Mn. I consulted the great steel metallurgist of the day, Alexander Holley, who listened attentively to what I had to say, and told me he did not think my plan was practical, so I abandoned it for the time being. But I was so stubborn that I could not get the notion out of my head. It seemed to me that a good metallurgist should be able to work the thing out in some way. I had already had some experience in smelting refractory lead ores in Utah, and was young and not lacking in self confidence, so after waiting a bit, I got Anton Eilers, the best all-around metallurgist I knew, and J. H. Bramwell, the best iron blast-furnace man I knew, both intimate friends of -mine, to come to my place in Bartow County, Georgia, and look over things. They remained for several days, and made all the examination they thought necessary; and they also advised me to give up the project, and either to keep the furnace running on car-wheel iron or to blow it out. After my talk with Holley, I improved my plant in several ways. I closed the top of the furnace, put in a hot-blast stove, a steam boiler and a Weimer blowing-engine which gave me blast enough, at a pressure high enough for all the requirements of, the furnace, and which I could bring up to a temperature of 600° to 700° F.

Jan 1, 1921

By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines&apos; Monograph 7.&apos; An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines&apos; Monograph 7.&apos; An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.&apos;-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc&apos;s were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967