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By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961

By H. R. Brannon, R. J. Robinson, G. W. Kattawar

Accurate prediction of storm wave characteristics are needed for design of offshore structures. Statistical methods of random noise analysis provide techniques for predicting required wave properties. These techniques have been used to analyze and characterize storm wave profiles from Gulf of Mexico recording installations in 34, 65 and .98 ft of water. Correlations based on the results can be used to predict wave crest probabilities and wave shapes for a range of Gulf water depths and storm conditions. Example predictions of wave crest probability as a function of water depth for a particular set of storm conditions are given. INTRODUCTION Accurate predictions of wave crests and wave shapes are needed for design of offshore structures. With predictions of wave crests, platform deck elevations giving adequate protection from exposure to storm waves can be selected. Use of hydro-dynamic wave theories with the wave crest and wave shape predictions permits an estimate of the wave forces an offshore structure must withstand. Observation of ocean waves suggests use of statistical analysis for studying wave characteristics for water depths beyond the breaking wave zone; recent wave generation theories lend support to this approach. l-3 One of the most powerful methods of statistically analyzing wave profiles was introduced by Cartwright and Longuet-Higgins; most of the basic relations used were developed by Rice5.6 in studies of random noise theory. This method predicts wave crest elevation probabilities from two parameters characterizing a wave profile. The statistical approach also provides a means for predicting wave shapes. In the random noise model of a wave profile, surface elevation is represented as an infinite sum of sine waves with closely spaced frequencies and random phase angles. Power density is proportional to the sum of the squares of the amplitudes of sine waves having frequencies within a narrow band, and the distribution of power density as a function of frequency is called the power density spectrum, or power spectrum. The power spectrum characterizes an irregular sea, and hence finds use in motion studies of ships, barges and semisubmersible drilling platforms. From the power spectrum, a wave profile of any duration of time can, in principle, be calculated; this long wave profile depicts the many wave shapes to which a structure may be exposed. Thus, the statistical methods of wave analysis provide an approach to selecting wave shapes as well as wave crest elevations needed for design of offshore structures. For practical application of these techniques, power spectra and related quantities must be predicted from storm properties. Barber and Tucker 7 have reviewed correlations of wave properties and storm conditions. Their review summarizes work of Darbyshire,8 among others, in which a correlation of power spectra with wind intensity of the North Atlantic was developed. These results, plus more recent work by Pierson and Moskowitz and Kitaigorodskii,10 establish feasibility of correlation, but there is no theoretical basis for modifications extending the relations to other areas as remote as the Gulf of Mexico. Hence, to predict characteristics of Gulf of Mexico waves, a study of local observations is needed. This paper presents (1) a practical approach to computing wave profiles hat depict shapes of waves for use in force calculations, (2) a summary of relations for predicting probabilities of wave crest elevations, (3) correlations of parameters needed to apply these methods in the Gulf of Mexico and (4) examples of application of the techniques. THEORETICAL BACKGROUND The following sections summarize relations needed to calculate wave profiles and to estimate wave crest probabilities. These relations also identify quantities that must be related to storm

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By J. M. Campbell, T. S. Buxton

The most widely used methods of predicting the volumetric properties of gas are based on the principle of corresponding states, which asserts that the compressibility factor is a universal function of reduced temperature and pressure. Previous studies have shown that the acentric factor, as proposed by Pitzer, l is an important addition to reduced pressure and reduced temperature as factors affecting the compressibility factor. Results of this study indicate that, if the pseudocritical temperature and pressure used to determine the reduced conditions are adequately predicted, characterization of natural gas-carbon dioxide mixtures with the acentric factor will allow reliable determination of the compressibility factor. Comparisons of predicted and experimental compressibility factors have shown that the pseudo-critical constant rules of Stewart, Burkhardt and Voo 2 are satisfactory for hydrocarbon mixtures. However, these rules fail to predict the pseduo-critical constants for hydrocarbon-carbon dioxide mixtures. Based on graphically determined pseudocritical temperatures for binary hydrocarbon-carbon dioxide mixtures, a correlation which gives the required correction to the Stewart, Burkhardt and Voo rules was prepared and a compressibility factor prediction technique was proposed. To test the proposed technique, compressibility factors for live mixtures of methane, carbon dioxide and either ethne or propane were experimentally determined at 100, 130 and 160F and pressures up to 7,026 psia. The predicted and experimental compressibility factors for these live mixtures had an average absolute deviation of 0.55 percent. INTRODUCTION Two-parameter generalized correlations based on the principle of corresponding states (PCS) are presently available for reliably predicting the compressibility factor of lean natural gas, i.e., natural gas with low concentrations of hydrocarbons heavier than methane. When these same correlations are used for mixtures of natural gas and carbon dioxide, large deviations between actual and predicted compressibility factors are observed. This study was undertaken to provide a means for accurately predicting the compressibility factor for such mixtures. In the past, two avenues of approach have been employed to extend the applicability of the PCS. The first has been to introduce additional parameters. The second has been to develop combination rules for predicting pseudocritical constants which do not suffer from the limitations of the commonly used molal average constants. In this study, both of these approaches have been considered and employed to arrive at a method for predicting the compressibility factor of mixtures of hydrocarbons and carbon dioxide. SELECTION OF A THIRD PARAMETER Failure of the original PCS to predict the compressibility factor for all pure gases, regardless of their mass, shape or polar moment, has led to the introduction of additional parameters into the PCS. Parameters have been introduced to correct for quantum deviations,3-5 non-spherical or globular shapes6-9 and for polar moments.8-12 In addition to these parameters which are based on some microscopic property and intended to correct for some specific cause of deviation, more general parameters based on some bulk property have also been introduced.1913-16 To use additional parameters to correct for each of the possible causes of deviation among the individual constituents of a gas mixture would require a rather complex form of the PCS. To maintain the PCS in as simple a form as possible, it is more desirable to have a single third parameter which is based on some bulk property influenced by several of the factors causing deviations. The third parameter selected for use in this study is a factor originally proposed by Pitzer.9

By S. J. Rothman, L. T. Lloyd

S. J. Rothman and L. T. Lloyd (Argonne National Laboratory)— Hagel's paperz0 discusses the question of the mechanism for self-diffusion in bcc transition metals. Recent work21"23 has led us to agree with him in reabandoning the ring mechanism in favor of a defect mechanism, most likely vacancies. On the other hand, we think that Hagel's attempt to group together all self-diffusion in bcc transition metals is wrong. We prefer the scheme of Peart, Graham, and omlin," who separate them into two groups. One group contains the anomalously behaved metals P titanium,', y uranium, and perhaps zirconim.' The other group contains a iron," this alloy was held at 1800°C for 2 hr before quenching, its structure was all a. B. C. Giessen, I. Rump, and N. J. Grant (Authors' reply)—We very much appreciate the discussion by Deardorff and Kato regarding the a to /3 transformation temperature of hafnium. In the W-Hf program, as well as in a current study of the system Cr-Hf, standard precautions were exercised against contamination, including vacua of less than 10"5 mm Hg and a weight control check of all specimens to insure an impurity rise of less than 100 ppm. Following receipt of the above discussion, a revision was made in the annealing process. Arc-cast specimens were etched with a 10 pct HF-90 pct HNO solution until 1 mm of surface, including a possible oxide film, was removed. Annealing was done in a hafnium container which provided a long diffusion path for gaseous contaminants. Finally, the heat treating time was shortened. Structural changes were noted to occur quite slowly. A 99.5 at. pct Hf alloy showed 70 pct /3 after 30 min at 1700°C and was 100 pct /3 after 10 min at 1715°C. After 24 hr at 1740C, the alloy was found to be 10 pct/3. This change is due to contamination; it was estimated that it corresponds to an increase of 60°C in the transformation temperature over a 24 hr period. The corresponding change in 30 rnin would be slight. Using the same hafnium as in the above publication, and three new alloys at 98, 99, and 99.5 at. pct Hf, the transformation temperature was indicated to be 1715" 15°C. Since this hafnium contained 4.4 at. pct Zr, a correction of 40 5C, based on an assumed approximately linear transformation temperature curve, must be made for pure hafnium. This yields a value of 1755 20°C in good agreement with Deardorff and Kato's value. Because the slope of the boundary is small, this permits a good extrapolation, and we regard the W-Hf alloys as well suited to check the Hf transformation temperature. niobirn,'' and molybdenum,22 whose activation energies correlate with the melting temperature and whose Do values follow Zener's predictions.28 We have no quarrel with Hagel's placing chromium into the second group; we disagree with his interpreting our data to make uranium fit into that group. Hagel considers that the measurements of self-diffusion in uranium below about 950°C represent combined volume and grain boundary diffusion. This contention is based on the curvature of the penetration plot for our 891°C run,4 which also has a nearly straight line plot of log c vs x. Hagel has extrapolated these characteristics to our 803.5C run and fitted his Arrhenius plot for self-diffusion in y uranium to our four highest temperature points only. We think this is wrong for the following reasons.

Jan 1, 1963

By C. Feng

HE sensitivity of twinning in molybdenum alloys containing 20 or more at. pct Re was reported by Dickenson and Richardson&apos; and Sims et a1.&apos; The latter3 also studied the effect of twinning on plastic deformation of these alloys. Recently, in this laboratory, the twinning planes in a series of Mo-Re alloys were successfully identified by tracing their boundaries on two known surfaces of the crystals, with the aid of stereographic projection. The nominal alloy composition and the results of the determination are listed in Table I. Metallic powders of molybdenum and rhenium with 99.9 pct purity were mixed, pressed and arc-melted into buttons under purified argon in a water-cooled copper hearth; the buttons were annealed at 2400 °C in vacuum (10-&apos;mm Hg) for 1 hr, remelted under argon and finally reannealed in vacuum at 2400°C for another hour. This treatment yielded a homogeneous alloy. Large-grain specimens devoid of subgrains were obtained with grain diameter varying from 1/8 to 1/2 in. A typical specimen weighed about 15 g. Orientations were determined by taking X-ray back reflection photographs for each grain on a polished surface of the specimens. Two surfaces were cut and polished; the angle between the two surfaces was measured with an accuracy of *2o. The twins were produced by compression in a hydraulic press at room temperature. Usually, several sets of twins could be obtained within each grain. Except in cases where no twins were formed, (Crystals 7, 8, and 9) the twinning planes were identified consistently as the (112) family over a wide range of alloying compositions and surface orientations of the crystals, as indicated in the stereo-graphic triangle in Fig. 1. The twins, however, were not broad enough to accommodate a conventional X-ray beam and no identification could be made of the twinning direction. Nevertheless, the direction must be one that lies in a plane of symmetry perpendicular to the twinning plane. There are only two such possible planes in a bcc lattice, namely the (110) and the (100) planes. Of these, only the (110) planes are perpendicular to (112), and the <111> direction is the intersection of the two perpendicular planes. It can thus be concluded that <1l1> is the twinning direction. The twinning elements of molybdenum have been reported as the (112) planes and the <111> directions,4 which are also the operative elements in other body-centered-cubic metals, such as W, a-Fe, and ß -brass.5 Thus, the present finding of the twinning elements in Mo- Re alloys supports the concept that twinning formation is mainly governed by the lattice structure. It is of interest to note that for specimens containing 12 at. Pct Re or less, no twins were found after being plastically deformed to as much as 30 pct reduction in height by compression, while for the 35 at. pct Re alloy, twins were formed with less than 1 pct deformation. This, of course, does not exclude the possibilities that for Re-Mo alloys containing 12 pct Re or less, twins could be formed under different conditions, such as at liquid air temperature or under impact loading. The present results, however, suggest that under the same conditions twinning is increasingly sensitive with increasing rhenium content. Consequently, the plastic strain at which twinning starts was found inversely proportional to the amount of rhenium in solid solution with molybdenum. This plastic strain necessary to cause twinning may be used as a criterion in the study of twinning characteristics.

Jan 1, 1961

By Charles L. Thomas

A novel, highly sensitive, and reproducible nzetlzod for the determination of hydrogen in solid materials is presented. The procedure requires equilibration of the specimen with hydrogen gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subse-quent quantitative analysis by mass spectroscopy. Good linearity is obtained for the Arrl~enius plots of the investigated metals. The advantages in the use of this method over that of Sieverts aye discussed. The solubility data for copper are in reasonable agveewzent with a considerable number of other inuestigations, wllile those fov silver are considerably lower than previously reported. The first known solubility data for gold are presented. Solubility equations and heats of MUCH of the data which are available on the solubility of hydrogen in various metals and alloys have been obtained by the classical Sieverts method.&apos; The method involves the measurement of a decrease in pressure of a gas in a calibrated system, and the calculated contraction in volume is attributed to the solubility of the gas in the metal sample. The procedure requires several corrections, such as the solubility of the gas in the container walls and the diffusion of the gas through these walls, as noted by Steacie and .Johnson2 and others. In addition, errors may be incurred due to reactions between metal surface impurities, such as oxides, and the saturating gas. The precise calibration of the measuring system where large thermal gradients exist can present additional difficulties. Also, accurate volumetric measurements of small quantities of gas are difficult. Many of the objections to the Sieverts method were overcome on solid materials by Ransley and ~eufeld,~ who first saturated the metal with hydrogen and performed a subsequent extraction and measurement of the gas by chemical means. Eichenauer and pebler4 and Eichenauer, Kiinzig, and pebler5 measured the diffusion coefficient and solubility by following the degasification of a sample as a function of a rate of increase in pressure in a previously evacuated system. Here again, however, the procedure involves many of the corrections of the Sie-verts method. The present investigation deals with the solubility of hydrogen in solid copper, silver, and gold by a technique which eliminates many of the aforementioned corrections and possible errors. This procedure requires equilibration of the specimen with gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subsequent quantitative analysis by mass spectroscopy. EXPERIMENTAL Two completely separate systems were employed to accomplish first, the equilibrium saturation of the sample and second, the extraction of the dissolved gas. Saturation Apparatus. The saturation apparatus, illustrated in Fig. l, consisted of a vertically mounted quartz tube with a three-way valve for vacuum or hydrogen near the top and an outlet near the bottom leading to a butyl phthalate seal. The bottom end of the tube was terminated with a joint accommodating an O-ring sealed "Asco Stirring Gland" (The Emil Greiner Co.). This gland facilitated movement of the thermocouple without introduction of air into the system. The upper portion of the tube (above the furnace) was water-jacketed. A Welsh 1405-B mechanical pump provided the necessary system evacu-

Jan 1, 1968

By P. Hudock

Thin films of PbS and CdS have been deposited on insulutiug- sapphire substrates by euzploying a subliwzation technique rising near-equilibriurum conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have mobilities approachitzg values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. By performing the depositiotz of a compound within a small chamber heated to a UNiform temperature within a Vacuum systerrz, it is possible to approach equiilibrium cod-tions r.~litl~irs the chamber. In this way; the sublimation and condensation proceed under near equilibrium co?zditions, and it was found that the properties of dePosited corrzpounds were similar to those of the source material. Oriented PbS films on sapphire have a roor?l- temperature unobility of 700 sq cm per v sec and a T-5/2 temperature dependence characteristic of bulk crrystnls. CdS layers on sapphive Izazse a resistivity ~uhich is corrlpamble to the resistivity of the souvce crystals over a range of four ordem of rrlagnitude. Irz contrast, Ihe resistivity of CdS films prepared by conventional evaporation depends largely upon the substrate terrzperat~ire and postheating treatrrletlt, vather than upon the properties of&apos; the solirce rrraterial. In the case oj the CdS films the achievment of high carrier mobility required the cargful exclusion of cont~~~~ii~unts from the films. The steps taken to accomplish this included presublimation of the source material, performance of the deposition at a backg-m~ozd pressure less than 10-8 Torr, and a solvent extraction with liquid cadminum, similar to that described by Aven and woodbury. The deposition of ,films under near-equilibrium conditions is being op-plied to other classes oj COmpounds. II should he of 1:allce ,tor llle deposition of nny matevial that decomposes in the vapor state. THIN films of PbS and CdS have been deposited on insulating sapphire substrates by employing a sublimation technique using near-equilibrium conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have Hall mobilities approaching values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. Depositions were performed in a small quartz sublimation cell shown in Fig. 1 that contained the compound and the single-crystal sapphire substrate. The substrates were etched in tapered solutions of hot phosphoric acid, rinsed in deionized water, dried, and transferred to the cell under dry nitrogen. Graphite crucibles and substrates were used in experiments where it was necessary to provide an inert test vehicle for the analytical determination of impurities in the source crystals and deposited films. The crucibles and substrates were machined out of spectrographic-grade graphite having less than 1 ppm of impurities. A quartz mask was sometimes used to define a pattern which could be used for Hall and resistivity measurements. Close spacing between the compound and substrate was maintained to insure better transport of each component from the source material.

Jan 1, 1968

By K. H. Adams, T. Vreeland

The basal stress-strain behavior, dislocation density, and strain vale sensitivity of the flow stress uqere measured at room temperature on single crystals oj-zone-refined zinc , 99.999 pct Zn, and zinc containing 0.0025 and 0.02 wt pct Al. No significant change in the stvain rate sensitivity of the flow stress occurs with the addition of aluminum. Changes in dislocation substructure and nonbasal dislocation density were obserrled with the addition of aluminum. The effect of aluminum on the basal slress-strain behavior is explained in terms of changes in nonbasal dislocation density which determines the separation distance of junctions between basal and nonbasal dislocations. The onset of basal slip is associated with the breaking of attractive junctions. The chunge in basal dislocation density was found to be proportional to the one-third power of the plastic shear strain, indepedent of purity. THE effect of impurities in solid solution on the stress-strain behavior of single crystals has been the subject of many theoretical studies. These studies have generally concentrated on the interactions between impurities and dislocations to explain the hardening effeet of impurity additions. The theories that have been proposed include those of yott and Nabarro,&apos;l&apos; Cott-re11; Suzuki; and Fisher. In practice, it is generally difficult to predict the relative importance of the vari- ous effects due to impurities. In addition, secondary effects of impurity additions such as induced changes in dislocation density and substructure in the as-grown crystals have received little attention. Many experimental investigations have been conducted on the effect of impurities on the stress-strain behavior of fcc crystals. Hcp crystals have not received much attention except for the extensive work of Levine et a1.= on magnesium alloy crystals. Stuwe~&apos;&apos; has studied the effect of copper impurity on the critical shear stress of zinc crystals and has interpreted the results in terms of the impurity atmosphere model of Cottrell and Jaswon. This report presents the results of an experimental study of the effect of aluminum additions to zinc on the basal stress-strain curve and the strain rate sensitivity of the flow stress. Etch pit techniques were used to measure and characterize the dislocation density and substructure in the zinc alloy crystals. EXPERIMENTAL PROCEDURE Specimen Preparation. Compression test specimens of four different purities of zinc were prepared from CP grade zinc of 99.999 pct purity obtained from the New Jersey Zinc Co. An analysis of this material furnished by the supplier indicated the following impurities in wt ~ct: Pb = 0.0002; Fe = 0.0002; Cd = 0.00005; other <0.60011. A quantity of material of this grade was further purified by zone refining. Zone refining was carried out under a helium atmosphere by passing a double &apos;One furnace Over a 6-ft-10ng charge at the rate of 2 in. Per hr. * total of ten double zone passes were made before the charge was removed from the furnace. The first one third of each charge was used to grow single crystals. Quantities of two

Jan 1, 1969

By Franz Fohr

On July 27, 1919, there passed away a simple, unassuming gentle-man, who, throughout his life, allowed his intense modesty to keep him-self in the background and during his later years effaced himself so thoroughly that but few of his acquaintances knew aught of him. Yet he was one of our accomplished metallurgists, who did good work in the practice of his profession and lived an upright life. Now that he is no longer with us Franz Fohr cannot plead to be overlooked, and those who fondly remember him will be gratified by his receiving his due. Franz Fohr was born, Sept. 7, 1838, in Mannheim, Germany. Of his ancestry, education, and early career we know scarcely anything. We do not even know just when he came to America, or. what led him hither. The first record of his professional work in this country, found among his papers, shows that from July, 1870, to Jan. 1, 1872, he was superin-tendent of the Newark Smelting & Refining Works, then owned by Ed-ward Balbach & Son. At that time the Balbach works at Newark, established in 1850, and the Selby works at San Francisco, established about 1866, were the only important silver-lead refineries in the United States. Mr. Fohr may have been associated with the Balbachs for some time before he became superintendent of their plant or he may have come from Germany but a short time previously. At all events, it is certain that he was at that time an experienced and accomplished metallurgist. After leaving Newark and going to San Francisco, he soon formed a connection with Thomas H. Selby & Co. Early in 1874-this firm sent him to New York to procure information respecting the manufacture of white lead. His engagement in New York terminated on-Jan. 31, 1875. During 1875, Mr Fohr spent some time at Silver Islet and in the Lake Superior copper region, but of his work there no record remains. In the latter part of 1875, or early in 1876, he associated himself as metallur-gist with the Boston Silver Co., operating at Saint John&apos;s, Summit County, in which William L. Candler, of Boston, was the moving spirit. That company was developing its mine in 1875. At the end of that year it "had about 800 tons of ore on hand, about three-fourths of which is dress-ing ore, to be concentrated in its very systematic establishment and to be smelted into pig lead." Evidently Mr. Fohr was engaged for the latter purpose. Henry A. Vezin, erudite and painstaking, was the mechanical engineer for the company. In the fall of 1876, Anton Eilers took his family for the first time so far West as Denver and Mr. Fohr went with them. I do not think that Mr. Eilers had any connection with the Boston Silver Co., save possibly in a consulting capacity, but he visited Saint John&apos;s and the enduring friendship among Eilers, Fohr, and Vezin, which terminated only with their deaths, dated from that time.

Jan 12, 1919

By W. R. Ingalls

Jan 1, 1922

By W. R. Ingalls

Jan 1, 1922

By E. W. Hart, W. R. Hibbard

The room temperature flow characteristics of a series of Cu-Cr alloys are found to be related to the amount and characteristics of the chromium-rich precipitate. The results are consistent with the theory of Fisher, Hart, and Pry, which considers the trapping to dislocation loops around precipitate particles. THE use of dispersed phases for hardening metals, particularly high temperature alloys, has been practiced for several years. Current theories describing the effects of dispersions on the basis of dislocation theory have been proposed by Mott and Nabarro.l-4 rowan," and Fisher, Hart, and Pry.8 These theories recently have been discussed by Hart,&apos; who pointed out that the experimental data available for comparison with theoretical calculations for overaged alloys are confined to studies by Gensamer, Pearsall, Pellini, and Low,8 Shaw, Sher-by, Starr, and Dorn,9 and some hitherto unpublished data on Cu-Cr alloys which will be described herein. Certain difficulties were associated with the interpretation of the first two studies. Gensamer, Pearsall, Pellini, and Low were concerned principally with interparticle spacing and did not document particle sizes. Shaw, Sherby, Starr, and Dorn included all the data in their report which was necessary for the theoretical evaluation, but their study is subject to some question1" due to difference in prior history of various specimens and due to systematic differences in particle characteristics" which appeared to be associated with differences in the magnification of their microscopic examination. The current study was undertaken to obtain critical data in a manner which avoids some of these limitations. Specimens of eight Cu-Cr alloys remaining from a previous investigation&apos;&apos; were available in the form of 100 mil sheet of the compositions shown in Table I. At 200 mil this material had been previously an- nealed ½ hr at 1000°C, water quenched, and cold rolled 50 pct. Samples were further cold rolled to a thickness of 20 mil for a total reduction of 90 pct. Sheet tensile specimens of standard geometry with a gage length 2½ in. long and 0.20 in. wide were machined from this sheet. These specimens were then annealed in a dried N2-H2 atmosphere for the times and temperatures indicated in Table I. This anneal served two purposes: 1—to obtain a fairly uniform and nearly constant grain size of 0.015 to 0.022 mm average diameter, and 2—to precipitate a fairly uniform, nearly spherical over-aged dispersion of essentially pure chromium. A typical microstructure illustrating the grain size and the uniformity of the dispersion is shown in Fig. 1. A typical dispersion illustrating the range of sizes and shapes of the particles is shown in Fig. 2. The tensile specimens were tested in the Instron equipment described in ref. 11 at room temperature at a strain rate of 0.04 in. per in. per min. Three tests were run on each alloy with sufficient repro-ducibility that a single true stress-true plastic strain curve could be drawn through the three sets of data for each alloy. Typical curves are shown in Fig. 3.

Jan 1, 1956

By Regis M. N. Pelloux, N. J. Grant

Five or six alloys each in the systems Ni-C.v, Ni-Mo, and NL-W, spaced to cover the single phase areas as well as a part of the adjacent two-phase field, were prepared as uacuum-melted alloys. Tensile tests at room temperature and stress rupture tests at 1200° and 1500°F we.ve run for time periods to give fracture in 0.1 to 500 hr. Observations mere made of solid-solution and second-phase strengthening or uleakening, coupled with studies of ductility and the role of structure on the noted behavior patterns. THE development of stable creep-resistant alloys while broad and systematic is also highly empirical. A number of simple rules have been suggestedL-" but these are based on scant data. Whereas rules for low-temperature alloy strengthening can be applied with some success in more simple systems, the extension to behavior at high temperatures (greater than about 0.4 of the absolute melting temperature) is very poorly understood and has encountered important exceptions and deviations in terms of atom size or valency effects. In particular, the occurrence of both solid-solution weakening4,5 and second-phase weakening2 at high temperatures is of interest. MATERIALS AND PROCEDURE Nickel was chosen as the base material because of its important role in current high-temperature alloy applications, because of its freedom from a phase transformation, and because of wide solubilities for many elements of interest. The selected alloys were single- and two-phase structures in the Ni-Cr,6 Ni-Mo,7 and Ni-w 8 systems. The alloys were vacuum melted and cast, utilizing high-purity raw materials, in the form of 15 lb ingots. They were readily forged into 1/2-in. bar stock (except the two highest chromium alloys). The alloy compositions are shown in Table I. Typical impurity values are: Carbon: Max 0.03 pct (except for 30 and 35 pct Cr alloys which had 0.07) Nitrogen: Max 0.005 pct (except for two of the Cr alloys which had 0.05) Sulfur: Max 0.004 pct Silicon: Max 0.05 pct Each alloy was solution treated (air quenched) to produce comparable grain size. The two-phase alloys were then overaged in an effort to produce a stable structure for testing at 1200° and 1500°F, The results are summarized in Table 11. Following the heat treatments outlined in Table 11, the bars were machined to a gage section of 1.25-in. long by 0.250-in. diam. In addition to room-temperature tensile tests, stress-rupture tests were run at 1200" and 1500°F for time periods from 0.1 to about 500 hr. RESULTS Room-Temperature Mechanical Properties—The ultimate tensile strength, total elongation, and reduction of area values for all the alloys are plotted vs atomic percent of the solute element in Fig. 1. It can be seen that for the same amount of solute element the ultimate tensile strength increases in the order chromium, molybdenum, tungsten. Elongation increases (reduction of area decreases) with increasing amounts of solute for all the solid solution alloys, the values ranging from 50 to 70 pct. The ultimate tensile strength values for the two-

Jan 1, 1961

H. Van F. Furman, Denver, Colo. (communication to the Secretary): There are some statements in Dr. Carpenter&apos;s interesting paper which appear to require explanation, if not modification.

Jan 1, 1901

By H. D. Outmans

In steady vertical flow, the interface of an immiscible liquid-liquid displacement is horizontal for any flow rate below the critical. In nonvertical flow, however, the shape of the interface in the steady state does depend on the flow rate, and the purpose of this paper is to calculate the unsteady interfaces during the transition of one steady state of flow to another. A knowledge of these transient interfaces is of considerable importance in reservoir engineering where the calculation of breakthrough recovery depends on the instant the interface reaches the producing wells and on the shape of the interface at that time. Although the emphasis is put on transient interlaces, which eventually approach stable equilibrium, it is shown that if the displacement exceeds a critical rate no equilibrium is possible. The interface is then unstable and viscous fingers are formed during the displacement. The critical rate and the shape of the transient and equilibrium interfaces are affected by the effective interfacial tension; but since this effective interfacial tension appears in the calculations only in combination with the inverse square of the thickness of the medium, its effect in the reservoir would appear to be negligible compared to its significance in model experiments. INTRODUCTION Stability criteria and the early growth of interfacial disturbances in a plane parallel to the boundaries of a dipping formation in which oil is displaced by an incompressible fluid were described in a previous paper.l This type of instability is significant in thin reservoirs. However, if the reservoir has appreciable thickness, then interfacial stability in vertical planes, normal to the upper and lower boundaries, also becomes important (the displacement is supposed to be parallel to these vertical planes). The difference between the two stability problems is that, in the first case, the intersections of the interface with planes parallel to the boundaries are normal to the direction of the displacement; in the second case, the intersections, this time with vertical planes, are not normal to the displacement. Instead, they are tilted at an angle which depends on the displacement rate. The tilt of steady interfaces was calculated by Dietz2 who also determined the critical rate of displacement for stability in the vertical plane by assuming that this rate would coincide with an interfacial tilt equal to the dip of the formation. The critical rate thus calculated is the same as has been found for thin reservoirs (see Eq. 1.1 of Ref. 1 and of the present paper). Dietz&apos;s calculation of the stable tilt was verified by laboratory experiments and the agreement was found to be fairly good.3 It is doubtful, however, that stable tilts actually exist in the reservoir because a change in production rate is not followed by an instantaneous adjustment of the interface to the new rate but, rather, by a transition period during which the interface changes from one equilibrium tilt to the other. The principal objective of this paper has been to describe these transient interfaces without putting any restrictions on the flow conditions or the shape of the interface, as had been done previously. The second objective was to compute the critical velocity, taking into account capillary effects, and the third was to evaluate, at least qualitatively, the shape of the front at rates above the critical, again without making the simplifying assumptions introduced by previous investigators.2,3 In the following sections two examples are given of the calculation of interfacial motion. The first describes this motion for an initially horizontal interface in a dipping layer, and the second for a vertical interface in a horizontal layer. The mathematical formulation of the problem is nonlinear in the boundary conditions, and this prohibits its solution in closed form. Instead, the solution is obtained in the form of higher-order approximations. 1 Before proceeding to a description of the mathematical model, however, we define two quantities

By Nicholas J. Grant, Olaf Troili, John Chipman

IN recent studies of the factors which affect the rate of desulphurization and its equilibrium, it became apparent that certain concurrent reactions were operative which had a significant effect on desulphurization. This is emphasized in the experiments of Hatch and Chipman1 and of Grant, Kalling, and Chipman&apos; by the slow approach to a final state of equilibrium which is in marked contrast to the initial rapid transfer of sulphur from metal to slag. Since the removal of sulphur is of such profound importance in iron and steelmaking, it appeared necessary to investigate the reactions responsible for this behavior. It is now known that the presence of iron oxide in the slag interferes seriously with the principal reaction of blast-furnace desulphurization: CaO (slag) +-S + C - CaS (slag) + CO [l] The interfering reaction is most simply expressed as: CaS (slag) + 0 = CaO (slag) +-S 121 and a small concentration of oxygen (or FeO) is sufficient to hold a considerable amount of sulphur in the metal. It has been shown by Grant, Kalling, and Chipman2 that the addition of MnO to blast-furnace slag slows the removal of sulphur from the metal. This effect overshadows the contribution of MnO to basicity and is ascribed to its oxidizing power. It will be shown in this paper that SiO, also has sufficient oxidizing power to interfere with blastfurnace desulphurization. This is, of course, only one of its several effects. Primarily it is an acid and therefore reduces the concentration of excess lime. But when silicon is reduced to the metal the oxygen to which it was previously bonded becomes in part available for reaction 2. The proof of this statement is found in the following experiments. Experimental Procedure and Results Utilizing the same procedure and apparatus described by Grant, Kalling, and Chipman&apos; five additional heats were made using slags IV and 11, the starting compositions of which were: slag IV—40 CaO, 10 MgO, 35 SiO,, 15 A1,0,; and slag 11—50 CaO, 10 MgO, 25 SiO,, 15 Al3O3. An important difference between these heats and those previously reported was that silicon to the extent of 1 to 4 pct was added to the present heats whereas the starting silicon content was formerly about 0.2 pct. Table I shows the slag and metal analyses for heats 82 to 87, and Table I1 shows the silicon addi- tions made to the charge. These additions are based on 400 g of metal and 400 g of slag. All heats had 1.65 400pct S charged before the cold slagadditions. The temperature was maintained at 1525°C. Rate of SiO, Reduction: Fig. 1 shows the silicon content of the metal in contact with slag IV at 1525°C as a function of time. Heat 70 from the work of Grant, afunctionKalling,of and Chipman is included as the lowest starting silicon. It will be noted that eeven with 4 pct Si in the starting metal, there is an increase in silicon content with time. Heat 84 is apparently approaching silicon equilibrium very slowly. Heats 70 and 82 with very much lower slowly.starting silicon show a more rapid initial rise in startingsilicon content but do not reach equilibrium during a long holding period. Fig. 2 shows 3 different initial silicon contents for Fig.2shows3differentheats 73 (from Grant, Kalling, and Chipman) 86 and 87, in contact with slag II, the most basic slag. Heat 73 is increasing in silicon with time, whereas heat 87 with an initial silicon content of 3.7 pct shows a decrease with time. Heat 86 shows a very close approach to equilibrium. The rate of transfer of silicon from slag to equilibrium.metal is very slow in all of those heats, even those which are initially far from equilibrium. ____

Jan 1, 1952

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-&apos; to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6&apos;9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3&apos;5&apos;7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5&apos;7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f &apos;([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1&apos; Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

Discussion of the papers of FREDERICH LAIST and HAROLD W. ALDRICH, FREDERICH LAIST and F. F. FRICK, W. L. AUSTIN, and STUART CROASDALE, presented at the Salt Lake meeting, August, 1914, and printed in Bulletins No. 91 and 92, July, and August, 1914. R. C. CANBY, Wallingford, Conn. (communication to the Secretary*). -Apropos of the experimental reduction of copper from cuprous chloride by fusion with ground limestone and coke, as described by Messrs. Laist and Frick, and also proposed for use at Chuquicamata., it might be of interest to refer briefly to the experience at Argentine, Kan., in the smelting of the suboxide of copper (as produced in the Hunt and Douglas process) containing appreciable quantities of chlorides. In the Engineering and Mining Journal of June 10, 1911, I. gave some account of what had appeared to be crucial difficulties with the Hunt and Douglas process, and how the filter-press difficulty had been so rapidly overcome after my discovery of the effect of the sodium salts in the leaching solutions. I also described the effect of the cupola furnace gases upon the lime rock with which I had replaced the coke in the absorption tower, which apparently showed the presence of considerable-chlorine, clue to the imperfect conversion of the subchloride to suboxide, as well as that clue to the difficulties of washing thoroughly the suboxide with the means provided, and also to the presence of chlorides in the cement copper which was smelted With the suboxide. The fumes from the cupola, when issuing direct into the atmosphere, were very dense and white, except when a hot furnace top caused a reddish tinge due to dust. These, fumes had a peculiarly suffocating effect, so that when they were blown over into the town the population suffered the greatest actual distress, not the mere annoyance which would have been clue to a disagreeable odor. The absorption tower had been built at the instance of the city authorities to abate this nuisance, and not with the idea of making any additional metal savings. A serious feature in connection with the Argentine experience with the Hunt and Douglas process was, that it had been implicitly assumed that there could be no metal loss in the Hunt and Douglas process itself, and that all attempts to locate the ruinous copper losses which were accumulating in the metallurgical accounts were devoted to the roasting department. It is possibly unfortunate for metallurgical advance along these particular lines that just about the time of this discovery of this previously unsuspected volatilization loss, in the smelting of the suboxide, the Kansas City company made a contract with the Western Union Telegraph Co. for its supply of copper sulphate and the Hunt and Douglas

Jan 11, 1914

(The paper by L. H. De Wald-Tech. Pub. No. 429 was presented at the Boston meeting, September, 1931.) W. A. SCHEUCH, Chicago, Ill.-Since starting up our Hawthorne copper wire plant we have found that wire bars from certain suppliers perform quite differently from those of other suppliers. In attempting to evaluate these bars, we made cross-sections, and in making these cross-sections we found considerable variation in the crystal structure. Indications were that there was some preference in the type of crystal structure. In attempting to find the reason for that we discussed it with the various producers and-also reviewed the literature. Mr. DeWald was assigned to determine the various factors that enter into copper wire bar crystal structure, on the basis that the product was a horizontally cast wire bar of practically identical composition and of recognized good composition for the present quality product sold in the market. Mr. DeWald has asked me to say that he should have made reference to Mr. Dalzell&apos;s paper on a theory concerning gases in refined copper. D. K. CRAMPTON, Marion, Conn. (written discussion).-Mr. DeWald has set forth an interesting and thorough exposition of the factors controlling macrostructure of this material. It is particularly interesting to us as it somewhat parallels work we have done on macrostructure of round copper billets for piercing into tubes. Our findings as to the effect of the several variables on macrostructure check Mr. DeWald&apos;s. The general principles underlying the two are precisely the same. The fact that we worked with copper deoxidized with phosphorous instead of tough-pitch copper, and round billets cast on end instead of wire bars, does not influence the results. We have found that round billets cast so as to produce large radial grains have greater soundness and density than those with a fine macrostructure. Further, and more important, we have found that the billets with large radial grains show markedly different performance on piercing from those having a fine equiaxed structure. With a given temperature of billet and adjustment of piercing machine, the coarse-grained material requires appreciably lower power for piercing and goes through the operation inn appreciably less time. These two differences are of sufficient commercial importance to warrant exercise of great care in maintaining the coarse structure. It seems probable that much the same phenomenon should hold in the hot rolling of tough-pitch wire bars. We would expect that, other things being equal, the coarse-grained wire bars would roll more readily and require less power than fine-grained ones. Moreover, we believe the differences in initial structure of the wire bars should be largely eliminated in the hot rolling process and during the subsequent drawing and annealing, of wire would be entirely eradicated.

Jan 1, 1932