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The Wednesday morning session was opened by President Stanley Shuhart at 9-30 a.m. He called the Chairman of the Auditing Committee. Kenneth Eaton, to report on the financial statement. Mr. Eaton read the data and asked for its approval. It was made, seconded and approved. John Turner, Chairman of the Resolutions Committee, submitted the following: RESOLVED: Whereas, in the year since the last convention of the Rocky Mountain Coal mining Institute, the Institute and the cool mining industry generally have suffered the loss through death of the services of: Walter M. Bellairs F. V. Colombo, M.D. George R. Delamater J. H. East, Jr. E. W. Felegy Hugo H. Machin Archie M. Morrison George E. Mills Veloy K. Piccioni

Jan 1, 1969

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.' When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.'4-'7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By Richards R. Vandervoot

T HE creep behavior of many polycrystalline metals at moderate stresses can be described by the empirical relationship: where Em is the minimum creep rate, A is a constant, a is the applied stress, E is the average elastic modulus at the test temperature, and D is the self-diffusion coefficient.&apos; This equation is generally applicable for strain rates of less than around 10-5 per sec and temperatures greater than about one-half the melting point in absolute units. Under these conditions atomic mobility plays an important role in the deformation process, and steady-state creep occurs when a dynamic equilibrium is reached between the generation and recovery of dislocation substructure. Although several theoretical mechanisms have been proposed to explain the creep of polycrystalline solids,2"4 the dislocation climb model2 is in accord with most experimental observations. The majority of creep data used to develop Eq. [1] came from metals with either the fcc or hcp crystal structures. However, on the basis of results for a and 7 iron as well as those for a and a thallium, Sherby concluded that the high-temperature deformation behavior of close-packed metals and bcc metals is probably the same.&apos; The greater creep resistance of fcc and hcp metals and alloys on a relative temperature scale was attributed to lower diffusivities in the close-packed structures. To further compare the creep properties of fcc, hcp, and bcc metals, creep data for all six bcc refractory metals were analyzed according to Eq. [I]. The results are shown in Fig. 1. The sources of information for the quantities used to prepare this figure are listed in Table I, except for high-temperature elastic moduli. The latter data were obtained from Refs. 28 and 29. The dashed lines in the figure represent the range and breadth of data analyzed by Sherby for fcc and hcp metals. In general, the deformation behavior of all of the refractory metals, ex- cept possibly that of tungsten, can be represented by Eq. [1]. This correlation is strong evidence of the similarity that exists between creep of pure close-packed metals and creep of pure bcc metals. At (Em/D) < 108, the results of Flagella and Tarr on tungsten (W-1 in Fig. 1) agree with the five-power stress law, while those of Green (W-5 in Fig. 1) show a seven-power stress dependence. Where (Em/D) > 108, the stress exponents for other data on tungsten were in the range 10 to 15. It is possible that the creep rate dependence on stress in this region is not a power law but exponential (i.e., Em - eßo). However, it was not feasible to differentiate between these two cases because of the steep slope and scatter in the data. Note the inflection point in the curve for the data of Flagella and Tarr (W-1 in Fig. 1). The slope of the line changes from 5 to around 10 at Em/D = 108. The breakdown of the fifty-power stress law at high stresses is not uncommon in other metals, and this phenomenon may result from nonequilibrium conditions in the material such as excess lattice vacancies produced by rapid straining.30 The mechanical strength of a polycrystalline metal is related to its microstructure. Attempts to establish the influence of grain size on the creep rate of metals and alloys have led to a wide variety of results. For example, the following effects have been observed: creep rate decreases as grain size increases;31&apos;32 creep rate decreases as grain size decreases;&apos;,33 creep rate is a minimum at some critical grain size and increases with either an increase or decrease in

Jan 1, 1969

By H. K. Kutter

The pressure pulse generated by an underwater spark \vas investigated in relation to its potential use for rock fragmentation. The study established (1) the relation between the peak discharge current and the peak wave pressure; (2) the relationships among the peak wave pressure, the discharge voltage, and the spark gap width; (3) the type and pulse duration of the generated wave; (4) the percentage of energy transmitted in the spark as a function of spark gap width and discharge voltage; and (5) the percentage of energy converted into the pressure wave as a function of gap width and discharge voltage. Spark-generated fractures were studied in two-and three-dimensional rock and plastic specimens. The laboratory results indicated that the pressure pulse generated by an underwater spark is a potential practical tool for rock fragmentation. The paper contains an appendix describing the capacitive pressure gage specially developed for the laboratory tests.

Jan 1, 1969

By G. Gutierrez, D. A. Elgillani, M. C. Fuerstenau

The zero-points-of-charge of apatite, calcite, and fluorite are pH 6.4, 10.8, and 10.0, respectively. Scheelite is negatively charged above at least pH 3. In this article, the flotation responses of these minerals in the presence of potassium oleate and sodium silicate are described and compared with electrokinetic data. Colloidal silica appears to be the species principally responsible for calcite depression, while silicate anion is the species responsible for fluorite depression. Additions as high as 1 x 10-3 mole/liter silicate have no effect on the flotation responses of apatite and scheelite. Selective flotation of nonmetallic minerals is difficult to achieve with fatty acids or soaps by themselves. As a result, specific reagents are added to aid these separations, and one of the reagents commonly employed for this purpose is sodium silicate. Flotation separations of various calcium-bearing minerals such as fluorite from calcite1-3 and scheelite from calcite2,4 and apatite,2,5 for example, almost always involve the use of sodium silicate. The mechanisms by which sodium silicate functions as a depressant are still not understood, probably for a number of reasons. For one thing, the dissolution process of sodium silicate is complex, giving rise to a number of ionic and colloidal species.&apos; Moreover, the type and concentration of these species depend on the ratio of Na2O to SiO2, the concentration of sodium silicate, and the pH of the system.&apos; At the present time, it is not known which species, colloidal silica or silicate anion, is responsible for depression. If colloidal silica is the species that is adsorbing, then adsorption must occur by electrostatic attraction between the colloid and the mineral surface. Silicate anion, on the other hand, may adsorb either physically or chemically. The objective of this paper is to determine first the active species of sodium silicate and then the conditions under which this species will adsorb and function as a depressant. EXPERIMENTAL MATERIALS AND METHODS Pure samples of apatite (Durango), calcite (Iceland-spar), fluorite, and scheelite were used in this investigation. Pure potassium oleate was used as collector, while reagent-grade HC1 and KOH were employed for pH adjustment. The sodium silicates used were samples obtained from the Philadelphia Quartz Co. In one series of experiments, various sodium silicates containing different ratios of SiO2 to Na2O were added to calcite systems. These sodium silicates contained SiO2-to-Na2O ratios of 3.75 to 1, 3.22 to 1, 2.40 to 1, and 1.60 to 1. All other experiments were conducted with the sodium silicate containing the ratio of 3.22 to 1, which is the one that is normally used in industry. Flotation experiments were conducted with 21/2-g charges of 48 x 150-mesh material in conductivity water with an apparatus and technique described previously. Electrokinetic experiments were conducted with both a Zeta Meter and streaming potential apparatus. Particle size was 48 x 65 mesh for the streaming potential experiments. EXPERIMENTAL RESULTS The first series of experiments involved flotation of scheelite in the absence and presence of sodium silicate. As shown in Fig. 1, flotation response was not affected with even the relatively high addition of 1 x 10-3 mole per liter sodium silicate. Interestingly though, no flotation was effected below pH 6 with this collector addition. The responses of apatite to flotation under these same conditions are given in Fig. 2. Similarly, no depression was obtained in basic media under these conditions. Similar experiments were conducted with fluorite, and in this case, depression was noted above about pH 11 with 1 x 10-3 mole per liter sodium silicate (Fig. 3). When calcite was floated with these same levels of addition of sodium silicate, essentially no flotation was possible above pH 7 (Fig. 4). The effect of collector addition with a constant addition of sodium

Jan 1, 1969

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.&apos;&apos; The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-&apos; "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By H. J. Engell, W. Frank, A. Seeger

SWISHER and ~urkdogan&apos; have determined the solubility of oxygen in a iron. They found it to lie between 7 and 10.5 at.-ppm at 881°C. Using earlier work on the permeability of oxygen in bcc iron,&apos; they arrived at the following expression for the diffusion coefficient of oxygen in bcc iron (k = Boltzmann&apos;s constant, T = absolute temperature): where The present authors3 have estimated the activation energy QD for the diffusion of oxygen in bcc iron in two different ways from various experimental data.2&apos;4"6 In the first method QD + QS (QS = heat of solution for oxygen in bcc iron in thermodynamic equilibrium with solid FeO) was determined either from data on the reduction of FeO with hydrogen4 or from measurements of the internal oxidation of silicon in a iron.5 Using an estimate of QS from investigations of the oxygen solubility in 6 iron2 (in thermodynamic equilibrium with molten FeO) Q = 0.97 ev or Q~ = 1.06 ev were obtained. From the magnitude of these values it was concluded that oxygen migrates interstitially in bcc iron and that consequently the activation energy QD for diffusion of oxygen has to be identified with the migration energy E~ of the oxygen atoms. Therefore, for a second estimate of QD from the diffusion coefficient of oxygen in 6 iron at 1450" ~,~ we used the theoretical expression:3 (a = length of elementary cube edge, m = mass of interstitially diffusing atom, sM = migration entropy), applicable to diffusion via the octahedral interstices in bcc lattices. Taking sM = 3.8 k (migration entropy of carbon in a iron), one gets Q = 0.90 ev. Hence, in Ref. 3 Q = (0.98 *0.1) ev was proposed as a plausible value for the diffusion energy of oxygen in bcc iron. sM + 9 (9 = solution entropy for oxygen in bcc iron) can be determined from permeability measurements.4 Using the above-mentioned estimate for QS , the following expression for the solubility c (atomic concentration) of oxygen (in thermodynamic equilibrium with solid FeO) in bcc iron was derived: From [4] the solubility of oxygen at 881°C in a iron is calculated to lie between 0.6 and 12 at.-ppm. We see that the solubility determined by Swisher and

Jan 1, 1969

By D. F. Kaufman, V. V. Damiano, G. J. London, L. R. Aronin

Beryllium bicrystals were Prepared by a seeding and floating zone-melting technique from high-purity beryllium single-crystal material. The starting material was given six floating zone purification passes prior to producing the bicrystals. Symmetric, asymmetric, and antisymmetric bicrystals were tested in tension. Included were bicrystals with boundaries both parallel and perpendicular to the tension axis. Modified symmetric bicrystals were also examined in detail. In these cases, the angles made by the slip planes with the boundary were not equal. Failure by (0001) cleavage, (1180) cleavage, and boundary separation were all observed depending on the orientation of these cleavage planes and the boundary with respect to the tension axis. Failure occurred on whichever system experienced the greatest normal stress. The origin of the fractures observed and the operative dislocation mechanisms were investigated by frac-tography and transmission electron microscopy. The results indicate that low-angle boundaries form in close proximity to the bicrystal boundary and act as sites for crack nucleation. It has been concluded that, although macroscopic compatibility was satisfied in many of the bicrystals examined, the bicrysta1 boundary was effective in Producing "early" failure by local bend plane formation as plastic deformation proceeded, followed by cleavage initiation and crack propagation. SINGLE crystals of high-purity beryllium oriented with the basal plane inclined 45 deg to the tension axis exhibit a critical resolved shear stress of about 300 psi and 200 pct extension by slipping only on the basal plane before failure by cleavage on that plane. Single crystals, oriented with the basal plane parallel to the tension axis, deform by prism slip at a critical resolved shear stress of 9000 psi and exhibit an extension of over 100 pct before failure in a ductile manner.&apos; In contrast to the behavior of single crystals, poly-crystalline beryllium deformed in tension or bending exhibits little or no ductility at room temperature. Beryllium&apos;s lack of ductility at room temperature has been attributed to its lack of a sufficient number of independent slip systems. Beryllium has only four independent slip modes at room temperature and according to the Taylor2 and von Mises3 criteria at least five independent shear modes are necessary to completely satisfy the strain compatibility conditions at all the boundaries in a random polycrystalline sample. Studies of beryllium bicrystals thus appear to provide a convenient way in which to determine whether the condition of strain compatibility is a necessary and sufficient condition to prevent failure and whether obviously incompatible boundary conditions result in boundary separation. Bicrystal studies, although not providing all of the constraints encountered in polycrystalline samples, do allow one to select very specific orientation relation-

Jan 1, 1969

By Northcutt Ely

My topic today is our Nation&apos;s interest in the minerals beneath the oceans. I will state what I think should be our objectives, the means available to attain these objectives, and the obstacles to their accomplishment. It is possible that as early as this year of 1969 our country must make policy decisions on this subject, and that these, once made, will be almost irreversible. Two factors are hastening an. early decision. First, the 1958 Convention on the Continental Shelf becomes eligible for amendment after June 10, 1969, if the Assembly of the United Nations so decides. Second, the United Nations has created a permanent committee of 42 nations, which was preceded by an ad hoc committee of 35 nations, to study the question of the peaceful uses of the seabed "beyond the limits of national jurisdiction. While these measures purport to deal with the creation of a regime to govern mineral development on the deep sea floor beyond the limits of the jurisdiction of the coastal nations, it has become clear that the urgent issue is the extent to which this future regime shall acquire jurisdiction over the mineral resources of the continental margin, and receive royalties therefrom. This brings the proposal into potential collision with the interests of the coastal nations under the 1958 Convention on the Continental Shelf, including, of course, the United States.

Jan 1, 1969

By Hetland Donald L.

Regional Tertiary formations and basins of local sedimentation which contain uranium deposits west of the Rocky Mountains are mainly of Oligocene, Miocene, and Pliocene age (fig. 1). The host rocks have been derived mainly from intrusive and extrusive igneous rock. The major host formations which cover broad geographic areas include the Esmeralda, Truckee, Humboldt, Thousand Creeks, Payette, Panaca, Cedarville, Coso, and San Joaquin Formations. Local areas of Tertiary sedimentation containing uranium deposits occur near Yuma, Safford and Artillery Peak, Arizona; Dillon and Canyon Ferry, Montana; Spokane Indian Reservation and Pend Orielle River, Washington; Topaz Mountain, Utah; Stanley Basin, Idaho; and Sonora Pass, California. Uranium deposits in these sediments have been classified into five categories based on environment (fig. 2). They are: (1) Deposits in lake sediments consisting mainly of water-laid tuffs; (2) Deposits in lake sediments intruded by volcanic plugs; (3) Deposits in lake sediments interbedded with arkoses near batholiths; (4) Deposits in coarse volcanic sediments in local sedimentary basins; (5) Deposits in arkosic conglomerates in local sedimentary basins.

Jan 1, 1969

The uptake of zinc, lead, and copper by the flora of the Tui Base Mine area near Te Aroha is described.Vegetation and soil samples were taken from two traverses across the Raukaka Lode. Results. after statistical analysis, indicated that Beilschmiedia tawa was a suitable species for biogeochemical prospecting for lead and that SchefJlera digitata was satisfactory for zinc.The tawa showed a negative anomaly for lead over the vein itself but not over the adjacent dispersion halo. It was concluded that lead concentrations greater than 230 p.p.m. in the wood ash of the tawa and zinc concentrationsgreater than 540 p.p.m. in the leaf ash of S. digitata denoted threshold values for anomalous mineralization in the soil beneath. Although both species contained copper, neither indicated a soil anomaly for this element.

Jan 1, 1969

By Niels Hansen

Dispersion-strengthened aluminum products consist of an aluminum matrix containing finely distributed ceramic or intermetallic particles. Examples of the two types of product are SAP, in which the dispersed phase is aluminum oxide, and materials made from atomized aluminum alloy powder, in which the dispersed phase can be FeA1, particles.&apos; A fundamental difference between the two types of product is that the elongation of aluminum/aluminum oxide products decreases with increasing temperature, whereas the elongation of aluminum- FeA13 products, like that of aluminum alloys, increases with increasing temperature. As regards the structural stability, aluminum/aluminum oxide products are stable to temperatures above 600° C as aluminum oxide does not react with aluminum, whereas prolonged heating at above 400°C of aluminum-FeA1, products leads to coarsening of the intermetallic phase and loss of strength.&apos; On the basis of these results it is supposed that a dispersion-strengthened product combining strength, ductility, and stability at elevated temperatures may be obtained if the dispersed phase reacts with the matrix in such a way that the reaction does not proceed at any significant rate at the application temperature. Different ceramic or intermetallic compounds may be selected as the dispersed phase, and, as alloying of the matrix phase may also influence the reaction, many possibilities exist for each metal. In the present study, aluminum products containing different oxides have been examined. For a reaction to take place between the dispersed oxide and the aluminum the free energy of formation of the oxide (MeO) must be greater than that of aluminum oxide; the difference should, however, not be too great in order to limit the reaction rate. Furthermore the aluminum alloy formed when aluminum reacts with the dispersed oxide should have a melting point near

Jan 1, 1969

A magnetometer survey &apos;was the Darkes Forest area between 1968. The instrument used was model MZ4 with sensitivity 9.4 conducted over part of 30th April and 3rd May, an ABEM torsion magnetometer gammas per scale division. The survey consisted of a closed magnetometer loop along lines cut for a previous magnetometer and seismic reflection survey by Wongela Geophysical in March, 1968. The magnetic results of the previous survey were not satisfactory in some areas and are presented as a comparison in instrumentation. Station separation in the present survey was 100 feet with tie-in readings at shot points of the previous survey (usually 1320 feet apart)

Jan 1, 1969

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By P. L. Raffo, T. E. Mitchell

Single crystals of Ta-Re alloys have been deformed in tension and compression as a function of solute concentration and temperature. The temperature dependence of the yield stress is decreased by alloying. At low temperatures there is a minimum in the yield stress (at about 2 at. pct) as a function of concentration. Three-stage hardening was not observed in the alloys. Linear hardening rates, where observed, were characteristic of stage II in pure tantalum. At low temperatures and high concentrations, work softening was often prominent at high strains. Electron microscopy revealed that dislocations are mostly of screw orientation, although heavily jogged and cusped, and often occurring in dipole pairs. The alloys become more prone to cleavage with increasing rhenium content, due mostly to an increasing yield stress rather than a change in cleavage strength. Alloying apparently decreases the Peierls stress of bcc metals at low temperatures by facilitating kink nucleation at solule atoms on screw dislocations. Higher solute concentrations further increase the yield stress. Quantitative calculations and comparisons with other bcc alloy systems are made to show that the predominant hardening mechanism is due to the interaction of dislocations with misfitting solute atoms close to their slip planes. The interaction is so localized that the core dilatation of dislocations could be important. CONSIDERABLE interest has arisen in recent years concerning the mechanical properties of unalloyed bcc metal single crystals.&apos;-7 These and similar studies on polycrystalline materials have resulted in a considerable understanding of the macroscopic yielding characteristics8, 9 and the process of work hardening.&apos;&apos; This latter advance is due in a large part to the increased use of transmission electron microscopy in P I RAFFO junior Membar AlMF is Metallyureist Iewis such studies and the general observance of three stages of work hardening in the shear stress-shear strain curves. The properties of substitutional alloy single crystals of bcc metals have not been determined in as much detail as in the pure metals. Insufficient systematic studies have been made on the effect of alloying on the magnitude and temperature dependence of the yield stress or the stress-strain curves. The alloy systems which have been studied to some extent have been Ta-W,11, 12 Ta-Mo," Ta-Nb,12&apos;14 Mo-Re,15 W-Re,16 and alloys of iron with nickel,17 platinum,17 vanadium,18 and aluminum.18 A large body of data exists on Fe-Si alloys, but these have mainly been a result of the experimental convenience of using this material in place of unalloyed iron, rather than a comprehensive study of the mechanical properties of the alloy system per se. The present authors have previously reported additional data on the properties of Ta-Re, Ta-W, and Ta-Mo alloy single crystals.1g Some of the data on Ta-Re alloys will be described later in this paper. Briefly, single crystals of Ta-Re (1.2 to 10.6 pct), Ta-W (6.2 and 10.2 pct), and Ta-Mo (2.9 and 9.0 pct) were grown by the floating zone method in vacuum. Compression tests were performed in the temperature range 77" to 623°K. Slip was found to occur in Ta-Re alloys at 77&apos; and 298°K on the (~ll)[lil] system and slip lines were coarser and straighter than in unalloyed tantalum. No three-stage hardening was observed in any of the alloy systems and the curves were nearly parabolic. At temperatures above 175°K the yield stress* increased monotonically with in- creasing composition while at 77" and 175°K the yield stress initially passed through a minimum after which it began to increase again for concentrations greater than about 2 pct Re. Similar minima were observed in Ta-Mo alloys and to a lesser extent in Ta-W alloys. The minimum was interpreted as being a result of a

Jan 1, 1969

By M. A. Dayananda

Based on the Kirkendall frame of reference, a method is proposed for the determination of atomic mobilities of all the diffusing species in a multicorn-ponent system with a single diffusion couple. The method is based on an atomic mobility model developed on the concept of negligible interactions among the intrinsic fluxes. It is shown in the model that mobilities can be obtained directly from the cumulative intrinsic fluxes past the Kirkendall interface. The proposed method replaces the need for a prior determination of interdiffusion coefficients far the calculation of mobilities. Relations between intrinsic diffusion coefficients and mobilities are derived and the mobility calculations are illustrated with diffusion data in Cu-Zn-Mn alloys at 850°C. ThE concept of "intrinsic flux" with respect to a fixed lattice was introduced "i Darken1 to explain toa Kirkendall effect2 demonstrated by the motion of inert markers during isothermal diffusion in single-phase binary solid solutions. Based on this concept, intrinsic diffusion studies have been made in various binary metallic systems3,4 employing such a lattice frame of reference, commonly referred to as the Kirkendall interface. Similar approaches, both theoretical and experimental, have been presented5"10 to study intrinsic diffusion in multicomponent systems. Based on the direct integration of Fick&apos;s law extended to multicomponent diffusion, Philibert and Guy8 proposed a method for the determination of intrinsic diffusion coefficients. For an n-component system, this procedure requires an experimental study with (n — 1) diffusion couples, all having their Kirkendall interfaces at the same compositio;, where n(n — 1) intrinsic diffusion coefficients are defined. This technique has been employed for ternary diffusion studies by Dayananda and Grace" and Guy and Leroy.11 A different approach is recommended by Ziebold and Cooper,12 who have derived relations between interdiffusion coefficients and atomic mobilities employing fluxes referred to the local center of volume. Their analysis is based on the simplifying assumption of negligible interactions among intrinsic fluxes. This assumption has been considered satisfactory for dilute solutions.5"7 The use of this analysis for the calculation of mobilities requires an initial determination of interdiffusion coefficients with a set of diffusion couples having intersecting diffusion paths. It is the purpose of this paper to propose a method that would permit a direct determination of mobilities of all components of a multicomponent system from a single diffusion couple. This method is based on a mo- bility model developed with diffusion fluxes referred directly to the Kirkendall interface, generally identified by inert markers. gen erall, like that of Ziebold and Cooper,12 employs the simplifying assumption that the flux of each component relative to a fixed lattice is caused only by the driving force of its own chemical potential gradient. THE KIRKENDALL INTERFACE Inert markers are employed in diffusion couples to locate experimentally the position of the Kirkendall interface. They are initially placed at the weld interface for "sandwich" couples, or at the original vapor-solid interface for vapor-solid couples. Studies of marker motion in binary systems3&apos;4 with both types of couples indicate that markers remain in a plane of constant composition and move with this plane para-bolically with time. Parabolic marker movements were also observed in ternary Cu-Zn-Mn couples by Dayananda and Grace.10 It is reasonable to expect a similar marker behavior even for diffusion couples with a higher number of components.

Jan 1, 1969

By W. K. Godfrey

The highest compressive strength cement has the highest bond strength in tests in which the cement is subjected to a confining pressure. After perforating, the bond strength is reduced to nearly zero when the pipe is supported by weak cement. Perforating does not affect the bond strength, however, when the pipe is supported by strong cement. Pipe supported by weak cement is damaged by perforating with expendable capsule jets, but is not damaged by perforating with the hollow carrier gun. High strength cements are recommended for oil wells that are to be perforated. Introduction The purpose of this work is to determine the effect of jet perforating on the bonding strength of oilwell cement at simulated down-hole conditions. Bond strength is a good criterion for determining the effectiveness of cement in performing its main function, i.e., that of isolating zones. According to the literature on the subject, the optimum cement strength for perforating is low and should not exceed 2,000 psi compressive strength. This conclusion was based on the appearance of bullet and jet perforations in neat and gel cements largely done in the absence of a confining pressure more than 15 years ago. Discussion Literature A relatively weak cement has been recommended in the literature as having optimum properties for perforating. In 1947, Oliphant and Farris tested bullet perforating of neat cements at various curing times.&apos; Some of the tests were made at down-hole conditions. They reported that the optimum cement strength for perforating was about 2,000 psi compressive strength. Enlarged holes occurred when strength was too low, and the cement shattered and cracked when the strength was too high. In 1951, Morgan and Dumbauld tested bullet and jet perforating of neat and gel cements at surface conditions.&apos; They reported that optimum cement has a compressive strength less than 2,000 psi. In their tests at atmospheric pressure, high strength cement shattered and cracked when perforated. Thus, the optimum cement strength was based on the appearance of neat and gel cement after perforating. In 1953, Clark showed a relation between cement strength and fluid shutoff.&apos; He concluded that a 500 psi compressive strength is required for good fluid shutoff and that maximum bonding ability is developed at approximately 1,000 psi compressive strength. In 1964, Bell and Shore invalidated most of the conclu sions by the previous authors when they demonstrated that atmospheric pressure tests cannot be used to determine casing deformation and damage that will result from perforating under down-hole conditions.&apos; They showed that the higher the hydrostatic pressure, the more restricted will be the expansion of gases generated by the charge. Less casing deformation and damage occurs under down-hole conditions than at atmospheric pressure. In recent work, Bearden et al. reported that jet perforating at surface pressure with the hollow carrier gun caused the cement sheath to shatter and crack.&apos; The perforating, however, did not seriously affect the pressure required to leak past the casing cement bond. Only three cementing mixtures were tested, and presumably they had strengths in excess of 2.000 psi. Bearden et al. also reported that the hydraulic bonding strength increased as the compressive strength increased. Their hydraulic test showed that approximately 1,000 psi pressure is sufficient to break the casing cement bond for a well aged neat Portland cement sheath. Unfortunately, the tests were not run with a confining pressure, so Bearden et al. were merely measuring the strength of their outer 8%-in. casing. In our investigation, we measured the hydraulic bond strength of cement to pipe under a confining pressure and found that the bond strength was not limited to 1,000 psi. Cement Bond The bond strength is a good criterion for measuring the effectiveness of cement in performing its main function, that of preventing interzonal communication of fluids behind the casing. Measuring bond strength after perforating should be a good quantitative method of determining optimum cement properties, and should be a better method than that used by previous investigators,11 &apos; who simply observed the appearance of the cement after perforating.

Jan 1, 1969

By Roy T. Southin*

The finding of Wojciechowski and Chalmers that columnar crystal growth can be stopped by an already existing network of equiaxed crystals is supported by other recently reported work on both static and mechanically stirred ingots.27,28 Support for the dendrite arm fragmentation mechanism, too, can be obtained by comparing the effects of spinning on ingots cast in a material which has a dendritic solid/liquid interface during solidification with one which has a cellular interface, since no evidence of change at the interface, other than a change in growth direction, can be found in the cellular material. But there are alternative ways of producing an equiaxed zone in materials which characteristically solidify with a cellular interface. For example, interrupted spinning of a normally cast ingot can do it. In this case it has been shown28 that the equiaxed zone is caused by the showing of dendritic particles from the top surface of the ingot to nucleate a network of equiaxed crystals which forms a barrier to the continued growth of the columnar grains. This showering has also been shown to be a major effect in materials solidifying with dendritic interfaces. It has also been proposed28,29 that, for an equiaxed zone to form, not only must nuclei be present ahead of the interface but also these nuclei must grow to sufficient size to be a barrier to the further growth of the columnar grains. A further requirement is that a network of these grains continually be produced ahead of the growing interface; otherwise there is a reversion to columnar growth as found by Wojciechowski and Chalmers. In normally cast ingots it is possible for nuclei ahead of the interface to grow since during a large portion of the solidification time there is no temperature gradient ahead of the interface,30 and, in fact, the liquid may be slightly undercooled.29 This then is the major difference between the work under discussion and normal industrial solidification conditions, since Wojciechowski and Chalmers imposed a considerable temperature gradient in the liquid. The statement in the Wojcieshowski and Chalmers paper that one needs to lower the temperature gradient

Jan 1, 1969

By W. H. Herrnstein, F. H. Beck, M. G. Fontana

Sulfur solubility in a iron was measured in the 750 to 890°C temperature range and was found to be insensitive to ferrite purity within a limited composition range. The permeability of sulfur in ferrite was determined from the internal sulfidation of Fe-Mn alloys. From the solubility and permeability results, the diffusivity of sulfur in ferrite could be calculated. These results are summarized as follows: Dissolved sulfur decreased the lattice parameter of ferrite. The effect of dissolved sulfur on the tensile properties of ferrite at low temperatures was also determined. SINCE sulfur is an important residual impurity in commercial irons and steels, effects associated with the presence of sulfur as a solute in iron are of considerable practical interest. Unfortunately, certain basic information relative to the Fe-S system appears to be lacking in the literature, e.g., the effect of dissolved sulfur on the lattice parameter and mechanical properties of ferrite. In addition, discrepancies exist in previously reported results for the solubility of sulfur in ferrite. These discrepancies raise questions regarding the sensitivity of sulfur solubility to the purity and microstructure of iron. This study was undertaken primarily in an effort to obtain reliable data on the solubility of sulfur in ferrite. Additional objectives included determination of the permeability and diffusivity of sulfur in ferrite by the internal sulfidation method and determination of the effect of dissolved sulfur on the lattice parameter and tensile properties of ferrite. EXPERIMENTAL METHOD Three grades of iron, encompassing a range of impurity levels, were employed in the study. The grades were designated VME (vacuum-melted electrolytic), SPZR (single-pass zone-refined), and MPZR (multipass zone-refined). The composition of each grade is given in Table I. Poly crystalline and single-crystal strip specimens were employed in the solubility experiments. Uniform grain size strip (ASTM 3 to 5) of 0.005 to 0.020 in. thickness was obtained by alternate cold reductions of 60 thickness 60 to 80 pct and recrystallization at 650°C for i hr in pure, dry argon. Single-crystal specimens were produced in 0.010-in.-thick SPZR iron strip by the strain-gradient anneal technique. Recrystallized strip 0.25 in. wide was strained until a Luders band or bands had propagated over the length of the strip; the strip was then annealed by drawing it through a 150°C per in. gradient (890°C peak temperature) at 1 in. per hr in an atmosphere of pure, dry argon. Laue photographs of the crystals produced exhibited no discernible asterism. Specimens were equilibrated with H-H, atmospheres at temperatures between 750" and 890" by one of two methods, each of which makes use of the reaction: The encapsulation sulfurization method was employed in the majority of the solubility experiments. A strip

Jan 1, 1969

By M. R. TECK, N. Rudd, L. K. Thomas, D. L. Katz

The authors are to be congratulated for presenting the first comprehensive paper on the theory and practice of threshold pressure determination in connection with underground gas storage. It is of particular value since most previous experimental work on this subject has been proprietary to the commercial laboratories engaged in such testing and to their clients. This dlscussion is presented in amplification of the subject paper, not in criticism, and is based upon our experience with approximately 5,000 threshold pressure determinations. Our comments are directed primarily to the experimental procedures as described by Thomas et al. It should be noted that, while clay mineral-rich lithologies are the most common caprock materials, the samples used (Table 1) include low permeability sandstones and carbonates, but do not include shales or other formations in which clav minerals exert a dominant effect. While our experience on samples analogous to those investigated by the authors generally confirms their findings, we have found that even more rigorous experimental conditions must be imposed where clay minerals are the controlling factor. These additional conditions result from the well-known molecular character of the clay minerals themselves in which water is interlaminated with, and bonded to, silicate sheets, thus becoming an essential component of the molecule. In many clay minerals the character of the intersheet bonding, and thus the dimension of the lattice, is strongly affected by variations in the identity and concentration of cations present in the intersilicate water. On a supermolecular scale, adsorbed water films on particle or "flakes" of shale provide much of the cohesive force necessary to maintain mechanical strength. The thickness of these films is variable and inversely proportional to intergranular pressure within the dimensional limits involved in caprock investigation. The thickness of the intersilicate water layers may also be subject to pressure under some conditions. These considerations are reflected in several necessary modifications of the experimental procedures described by the authors. Two of these are, in our judgment and experience, of such importance that they cast real doubt on the validity of data obtained on argillaceous materials without their application. The very careful resaturation procedures proposed by the authors should give good results in connection with the relatively "inert" lithologies used in their experiments. Our experience suggests, however, that they would create more problems than they would eliminate if applied to argillaceous materials. 1. Drying of the sample at the temperature and for the duration indicated by the authors not only will dessicate the sample with consequent shrinkage cracking, parting along bedding planes, and even total disassociation in the case of fissile shales, but it may also alter the character of the clay minerals themselves — in some cases irreversibly. 2. Prolonged evacuation to 2 microns Hg further dessicates the sample and is even more effective in reducing the intersilicate water content. 3. Resaturation with water differing in pH or chemical content from that existing originally in the sample also serves to alter the nature of the sample, particularly its structure and strength. 4. Our experience has been that, even with the thorough precautions proposed by the authors, complete resaturation of very fine grained materials is rarely obtained. Yet our experience confirms the

Jan 1, 1969