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Jan 1, 1968

By P. F. Gnirk

Consideration is given to creater formation with shallow, contained, chemical explosions in rock masses which exhibit different inherent physical and mechanical properties as determined by standard laboratory techniques. The primary purpose is to determine whether or not a simple but useful generalized correlation can be established between explosive crater formation and one or more common rock properties. Such a correlation could be beneficial in predicting with some degree of reliability the size of a crater which could be expected in a particular rock type for a given input of explosive energy. A series of crater formation experiments employing constant weight charges of Gelex 2 explosive was conducted in five submembers of the taconite formation at the eastern end of the Mesabi Range in northeastern Minnesota. Five mechanical and physical properties-unconfined tensile and compressive strengths, Young's modulus of elasticity, longitudinal wave velocity, and density-were determined by conventional laboratory techniques using core samples from the taconite submembers. Although insufficient data were obtained to warrant the use of mathematical methods in the determination of empirical relationships, the results provided a fairly strong indication that with an increase in magnitude of any one of the five rock properties definite decreases in the optimum crater volume and surface area occur. Furthermore, for a constant explosive energy input, the presence of bedding planes and joint systems in a rock mass influences the formation of craters in such a manner as to increase the volume of rock broken substantially above that expected from the same rock mass without joint systems and, in particular, without bedding planes.

Jan 1, 1968

By R. F. Stewart, A. W. Hall

A method has been developed for continuously measuring the moisture content of coal. The method is based on the thermalization of fast neutrons by hydrogen in the coal. Neutrons from a small radio-isotope source penetrate the coal, are scattered by hydrogen, and measured by a thermal neutron detector. The number of thermal neutrons counted can be directly correlated with the moisture content of coal. In a pilot-scale system, moisture was measured continuously within 0.2% in coal moving at rates up to 20 tph. The method is adaptable in industry for continuously measuring the moisture content of coal at high tonnage flow rates. Such an application would permit continuous recording of moisture in coal without sampling and facilitate quality control. An automatic and continuous method of measuring the moisture content of coal is needed by the coal industry. Automatic control of the coal quality would reduce the cost of coal preparation, improve the product, and thus indirectly increase the use of coal. Moisture in coal can be determined by several methods, but the time required to obtain samples and analyze them by existing methods makes it difficult, if not impossible, to control the quality of the product. Both producers and consumers need a method for continuous and instantaneous measurement of moisture content without sampling in order to regulate process equipment and keep the moisture content of coal within specifications. At the Morgantown, W. Va., Coal Research Center we are developing a nuclear method for continuous measurement of moisture in coal. This method is based on the thermalization of fast neutrons by hydrogen in the water and organic matter of coal. Neutrons from a small radioisotope source penetrate the coal, are scattered by hydrogen, and are measured by a thermal neutron detector. The number of thermal neutrons counted can be directly correlated with the moisture content of coal. Design of a moisture meter based on neutron thermalization depends on many variables, any or all of which can affect the sensitivity of the meter. These factors include those related to the nuclear aspect; type and size of neutron flux and source, type of detecting device, and background count; and those related to the coal being tested: rank, particle size, and ash content. A survey was initiated to eliminate the relatively insignificant factors and to ascertain the magnitude of the major effects. Such information was necessary to fully evaluate the technique and to establish design criteria. Coal contains a relatively large amount of hydrogen in the organic coal substance and the water of hy-dration of the shaly material as well as in the moisture. To apply this concept of moisture measurement to coal requires that the organic substance in coal from any one seam of a particular mine be uniform in hydrogen content. The difference in total hydrogen content of wet and dry coal is relatively small, so that a moisture measurement based on this concept requires a measurement between two large numbers to a high degree of precision. Thus, it was necessary to develop a highly precise instrumentation system for continuous measurement and to obtain a physical arrangement permitting measurement of moving coal with a minimum effect from density variation. EXPERIMENT WITH TRAYS OF COAL Tests were conducted with metal trays containing SO to 100 lbs of coal to develop an instrument system of high precision. A scaling system with a maximum instrument error of 0.2% was used to test different types of thermal neutron detectors. The most suitable type of detector was a boron-10-lined proportional counter tube. While this type of detector showed satisfactory stability, extensive testing disclosed a long-term count reduction probably due to some type of deterioration in the detector. However, development of an electronic system using dual detectors eliminated this deterioration as a serious problem. (The second detector would be used to measure a reference drum of dry coal — the difference in count rate between the wet coal and dry reference coal being a direct measure of moisture content.) Table I, column 1, shows typical results with a 1-curie plutonium-beryllium neutron source and a thermal neutron detector beneath a tray of coal and illustrates the precision of measurement. Consecutive measurements (indicated in Table 1, columns 2-5) of thermal neutrons at various times and positions be-

Jan 1, 1968

By Saluja, Sunder S.

Man had to learn to break rocks as early as the Stone Age, when they formed his main source of raw material. He started with chipping and over the years has reached a stage where he can employ atomic blasts and break, with one blast, millions of tons of rock. In between these two extremes there have been several stages of development including fire setting, use of the expansion of water on freezing in chipped cracks in cold climates, the use of low or deflagrating explosive black powder in about the 17th century, the use of high explosives with the discovery of nitroglycerine in 1846 by Sobrero, followed by the monumental discoveries of the great Swedish scientist Alfred Nobel in the latter half of the nineteenth century.

Jan 1, 1968

By D. G. Westlake

Levine has concluded that prismatic slip in titanium is controlled by two distinct thermally activated processes in the temperature ranges O° to 220°K and 220" to 300°K. We feel that his evidence is not convincing. He has drawn a curve through the plot of activation volume u* vs temperature T with a break at 22WK, Fig. 2. We believe that considering the possible experimental error apd the fact that there are only four points between 4° and 196°K, one could be justified to represent these points by the smooth curve we show as a solid line in Fig. 12. Levine believes that (8rf/aT)+ is discontinuous at 220°K, but he hints that he recognizes the possible doubt. We doubt seriously that the results shown in Fig. 1 indicate a discontinuity at 220°K. Certainly if he were justified in drawing a straight line through only four points on Fig. 2, we are even more justified in drawing straight lines through the seven points between 77" and 297°K on Figs. 1 and 3, because a straight line touches all seven of his circles. If his measurements of t were so precise that his decision to draw two curves in Fig. 3 is valid, then the experimental technique is deserving of further mention. We have drawn a smooth curve through the results in Fig. 3 and used this and the curve in Fig. 12 to obtain the values of shown in Fig. 13. Finding continuous is a contradiction of Fig. 4, which deserves comment itself. Levine obtained the solid circles in Fig. 4 using Fig. 2 and a smooth curve through the points shown in Fig. 3. We have replotted these solid circles in Fig. 14. We submit that there is no basis for his two straight lines (dashed in Fig. 14), and therefore have superimposed the curve that we believe is indicated. Certainly, there is reasonable doubt that a discontinuity in dH/dT exists at 220°K, even when one accepts Fig, 2. Furthermore, if one draws the straight lines indicated by least-squares treatments of the results presented as open circles in Fig. 4, their intersection is at about 196°K, not at 220°K as shown. Thus the alleged agreement between Figs. 3 and 4 with respect to "break" temperatures is not apparent. In Fig. 9, Levine has drawn a straight line very much different from the one indicated by a least-squares treatment. Obviously, he has done this because he recognized that H = 0 when T = 0. He is consistent in drawing the low-temperature curves in

Jan 1, 1968

By Hiram B. Woon

Uranium ore deposits in the Lisbon Valley area are in an arcuate belt, 15 miles long by one-half-mile wide, on the southwest flank of the Lisbon Valley anticline. They range in size from 500 to 1,500,000 tons and by mid-1965 had yielded 6,147,000 tons containing 48,530,000 pounds of U3O8. Ore bodies average 6 feet thick, are tabular, amoeba-shaped masses, concordant to the bedding, and are in the thickest, lowest sandstone unit of the Moss Back Member of the Chinle Formation of Triassic age. The host rock is predominantly a fluviatile, calcareous, fine-grained to conglomeratic sandstone. Uraninite, the principal ore mineral, fills the pores in the sandstone and partly replaces sand grains and fossil wood fragments. During Late Permian and Early Triassic time pre-Chinle Formations were arched to form the ancestral Permian anticline. Moss Back streams truncated Moenkopi and Cutler beds which capped the ancestral anticline and then covered it with fluviatile elastics, which were subsequently covered by thousands of feet of Triassic, Jurassic, and Cretaceous sediments. Uranium, probably derived from the Chinle Formation by diagenetic processes, was transported in connate ground waters, was moved by compaction or hydrostatic forces, and was deposited under reducing conditions. Uranium was emplaced around the crest of the ancestral anticline, prior to the Laramide orogeny. During the orogeny, the Tertiary-Lisbon valley anticline was super induced on the Permian anticline and, penecontemporaneous with uplift, was faulted parallel to its longitudinal axis. The Big Indian ore belt on the southwest flank footwall block was elevated to approximately its present position, and the northeast flank hanging wall block was elevated only slightly. An extension of the Big Indian ore belt around the northeast flank of the ancestral Permian anticline may exist in the Moss Back sandstone in the downthrown block northeast of the Lisbon Valley fault.

Jan 1, 1968

By H. A. Davies

DURING a current program of research on the structure and properties of liquid sodium alloys, the need arose for information on the solubilities as a function of temperature of several B subgroup metals in liquid sodium. In the absence of reliable information in the literature for several of these systems, par- ticularly at temperatures in the range 100° to 300°C, an apparatus was constructed to determine solubilities by a direct melt-sampling technique, followed by wet-chemical analysis for both sodium and the solute metal. The details of the technique have been described previously.' The solubility of indium in liquid sodium was determined at eight temperatures in the range 100° to 270°C. The solubility as a function of temperature is shown on Fig. 1; this represents the liquidus line over this composition range. A cooling curve was plotted after the completion of the sampling and an arrest was observed at 94.9°C which must be interpreted as being the result of a eutectic reaction. By extrapolation of the liquidus to this temperature, the eutectic composition was estimated to be about 0.25 at. pct In. The present estimate of the eutectic temperature and composition are in good agreement with the values of 96.0° to 96.2°C and between 0.28 and 0.45 at. pct In, respectively, which were reported by Heycock and Neville.2 However, no further information on the liquidus of this system at the sodium-rich end could be found in the literature for comparison. One compound: NaIn, has been reported in this sys-

Jan 1, 1968

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By R. B. Tippin, J. S. Browning

The feasibility of multistage heavy liquid cyclone beneficiation of spodumene was successfully demonstrated in this investigation. The indicated recovery for the multistage circuits was mathematically estimated as continuous test runs would be necessary to determine the true influence of a middlings recycle. In the three-stage circuit, both the concentrate analysis and spodumene recovery exceeded 90%. The two-stage circuits were unable to simultaneously yield an acceptable produce with a satisfactory recovery. With the Nation's growing industrial mineral requirements, the U.S. Bureau of Mines has undertaken the task of investigating new mineral dressing techniques and improving the existing concentrating methods of ore beneficiation. One such project is the gravity concentration of minerals using heavy liquid separation (HLS).1-3 Heavy liquid separation is based on the simple principle that a material, whose specific gravity is less than the density of a solution, will float on top of the liquid and a material with a greater specific gravity will sink. Heavy liquid separation techniques were developed in the laboratory over half a century ago but the process has yet to be commercially adopted. In the past, commercial operations have failed because of numerous problems.4 Industrial interest has recently been reactivated because of engineering advances. The number and quality of the heavy liquids suitable for mineral processing has increased while the cost has sharply dropped. New and improved liquid recovery systems5,6 are under consideration with present emphasis on 1) solvent extraction, 2) thermo-evaporation, and 3) water washing. The toxicity of the heavy liquids7 presents a problem, but throughout the chemical and mining industries, many similar hazardous materials are safely handled. A distinct advantage of using heavy liquids is its ability to provide a near perfect separation of fine-sized mineral particles even when the specific gravities are close. Effective separations have been made on minerals down to 200 mesh and with a density

Jan 1, 1968

By G. L. F. Powell

Bulk samples of silver have beat undercooled lo a large degree in contact with crystalline siliceous and ceramic oxide materials, indicating lhat stable oxides and oxide compounds are not the heterogeneous nucleants which normally catalyze cryslallization within a feu degrees of the equilibrium freezing point. Since 400-g samples were undercooled 250°C in contact with cristobalite, it is concluded that the undercooling required for homogeneous nucleation of sil11er is greater than 250°C. Undercooling was Jacilitated by precleaning the crucibles with a high-fires -sure blast of gas. IN numerous experiments on the undercooling of metal melts it has been assumed that a solid glassy surface, being non crystal line, will have no effect in catalyzing crystal nucleation from the melt. Conversely, it is usually accepted that any crystalline surface, in contact with a metal melt, will catalyze nucleation of metal crystals from the melt at degrees of undercooling less than that at which homogeneous nucleation will occur. Both these assumptions were implicit in the claim that homogeneous nucleation was observed in experiments1'2 on the undercooling of small metal droplets (10 to 100 mp diam). The droplets were thought to be freed of suspended crystalline particles which would otherwise catalyze heterogeneous nucleation. They were supported on flakes of silica glass which were assumed to be amorphous, and therefore incapable of acting as substrates for heterogeneous nucleation. In later experiments, large samples of molten metal were undercooled to temperatures similar to those achieved by the droplet technique by melting in a fused-silica crucible3 or a boro-silicate glass slag.4 Since these samples were usually fully enclosed in glass at the moment of freezing, it seemed possible that nucleation was homogeneous when maximum degrees of undercooling were achieved, despite the large size of the samples (up to 500 g). In experiments on the undercooling of silver5 the metal was contained in vitreous silica crucibles, the

Jan 1, 1968

By Roy P. Full, Robert M. Grantham

Regional structural adjustments in early Tertiary time resulted in the development of the Republic graben, a major down-dropped block that is from 6 to 10 miles in width and more than fifty miles in length. The graben became the center of extensive volcanic activity during Eocene and Oligocene time, resulting in a thick sequence of water-laid tuffaceous sediments, volcanic flows, and associated intrusives. A younger series of sediments, pyroclastics, and flows were deposited in structural depressions within the graben following the period of widespread volcanic activity. The Republic mining district is located along one of the major intragraben structural zones, where continuing subsidence during the period of volcanic activity resulted in an increased thickness of flows and associated flow breccias and pyroclastics. Intrusive masses in part healed early graben-forming faults, but later subsidence reopened old faults and created new fracture zones which later became the control for the gold-quartz veins. Considerable block adjustment along the subsidence area is evidenced by the structural pattern in the mines, and telescoped vein structures indicate north-south compressional stresses and east-west graben-forming tensional stresses prior to and during the emplacement of the veins. The veins, varying from a few feet to more than 50 feet in width, are filled primarily by fine-grained quartz, commonly chalcedonic or porcelain-like in appearance. Finely laminated dark-gray to black concentric banding within the veins generally distinguishes the better-grade ore zones, which contain finely disseminated sulfides and ore minerals that include principally electrum, stephanite, naumannite, and native silver.

Jan 1, 1968

By C. Laird, C. E. Feltner

An investigation into the effect of a material's slip character on its high strain fatigue properties has been carried out using copper and Cu-7.5 wt pct A1 as representative wavy and planar slip mode materials, respectively. In copper, the constant term and exponent in the Coffin-Manson equation, ?EpNf1/2 = const, are unaffected by the temperature of testing or the history of the metal. On the other hand, in Cu-7.5 wl pcl Al, while the exponent is invariant, the constant is increased with respect to copper and increased further with decrease in temperature. The life in Cu-7.5 wt pct A1 is double that of copper at room temperature and about four times at 78°K. Fractoflaphic studies indicate that these diffevences in life are associated with the early stages of cracking. In copper, severe surface rumpling provides crack nuclei at pain boundaries independent of' testing temperature or the history of the metal. In Cu-7.5 wt pct Al, the planar slip mode of deformation prevents grain boundary folding; crack nucleation is therefore mainly transgranular and the increase in life with respect to copper is associated with a prolonged linking-up stage of such transgranulay cracks. At the lower temperature the increased difficulty of cross slip inhibits multiplication of trans-granular cracks and retards the linking-up process, giving a further enhaancement in life. It is expected that such behavior will be found general in materials of wavy and planar slip mode, respectively. STAGE II crack propagation in high strain fatigue takes place by a repetitive process of crack tip blunting in the tension part of a fatigue cycle followed by resharpening of the crack in the compression part.1-3 This mechanism has come to be called the "plastic relaxation process".3 At very high strains (lives to failure less than 103 cycles), most of the life of a specimen is spent in crack propagation by the plastic relaxation process.4,5 Since the differences in the cyclic strain hardening behavior of metals and alloys are comparatively small in this strain range,6,7 the amount of blunting at a crack tip depends primarily on the applied strain amplitude. The rate of crack propagation in this life range is therefore nearly constant with respect to material and temperature of testing. In the longer life portion of the high strain fatigue range (l03 to 103 cycles to failure), a considerable fraction of the lives is spent in crack initiation and Stage I growth. Grain boundaries have frequently4,5,8 been found to be the sites for this growth which is also associated with a surface folding process.4'5 Such folding behavior may also be general in any material having a grain structure and capable of plastic deformation. It has therefore been suggested475 that the universality of the Coff in-Manson law,9'10 constant,* where ?Ep is the plastic strain range and Nf the number of cycles to failure, is reflected in the approximate invariance of both the crack initiation and propagation behavior. It happens that, in most investigations of the phenomena associated with failure,4,5,8 materials with a wavy slip mode have been used as vehicles for the studies, or else "normally" planar slip mode materials have been tested under conditions giving rise to wavy glide deformation, e.g., stainless steels cycled at high temperature.'' The purpose of the present investigation was to determine whether or not different cracking phenomena would occur when the slip mode of a material is planar and if the associated life to failure would be different than that of a wavy slip

Jan 1, 1968

By John M. Crowl, L. E. Sawyer

5.3-1. General Public Resistance to Strip Mining. Surface (strip) mining is the oldest recorded method of extracting coal and other minerals from the earth. This method of mining completely alters the topography of the earth's surface, leaving an area of more or less parallel ridges or of peaked mounds of the materials which overlay the mineral seam. It destroys all original vegetation and provides materials for new type soil. During the early years the acreage mined by this method was small, land was plentiful, and with a growing young nation no thought was given to the restoration of the disturbed areas to some form of productive use. Early in the present century the development of steam shovels and drag-lines made it possible to remove thicker overburden to recover the products. With the deeper digging, the size of the disturbed areas increased. With this increase in the size of equipment and the improvement of blasting techniques, mining was expanded into more prominent locations and to areas of more valuable land. The more progressive operators became aware of the need to reclaim those areas for some productive use. Electric shovels with capacities of up to 200 cu yd and draglines with capacities of 145 cu yd, capable of uncovering products over 100 ft below the surface, are now in use. Combined with the increase in the size of equipment, the expansion of contour mining or rim stripping in the mountainous areas has focused public attention on the need for a sound reclamation program for all disturbed areas. APPEARANCE. After mining, the areas consist of varying percentages of rock, shale, slate, and soil material devoid of all plant and animal life. Unless a definite reclamation plan is carried out, many of the mined areas will remain bare for a period of years. The topography of the area is completely altered. What may have been level to rolling land in cultivation, in grass, or in timber is thrown up into a series of ridges or mounds.

Jan 1, 1968

By Gerald J. Anderson

The Marquette District of Central Northern Michigan is the oldest of the Lake Superior iron districts with a mining history dating from 1852 up to the present. The total production of all types of ore through 1965 was 338,120, 146 long tons. Emphasis up to the 1950's was on mining the direct shipping ores; however, demands for higher-grade and better-structured ores in the last decade has resulted in a complete shift in emphasis to beneficiating the lowgrade Negaunee Iron-formation to produce high-grade iron ore pellets. The Precambrian sediments of the Marquette Range have been correlated with the Animikie Series of the Thunder Bay District, Ontario, and are contained in a westward plunging synclinorium that is approximately 3 3 miles in length and 3 to 6 miles in width. -The rock unit of major economic importance is the Negaunee Iron-formation that reaches a thickness of 2500 feet near the City of Negaunee. The primary iron content of the Negaunee Iron-formation averages 26 per cent, whereas the altered iron-formation approximates 31 per cent. The Negaunee Iron-formation has been divided into three principal types: diagenetic, oxidized, and metamorphic. The ores produced to date fall into four categories: high-grade soft ores, high-grade hard ores, siliceous ores, and concentrates and agglomerates (pellets). The soft ores generally are found in synclines and in fault-trough structures, bounded by mafic dikes along at least one side, and are mainly found in the basal portion of the Negaunee. In contrast, the hard ores occur in the uppermost portion of the Negaunee and are controlled by structural features such as folds, faults, and dikes. Iron-formation that has undergone diagenetic and metamorphic alteration makes up the main beneficiating ore types. Studies on the Negaunee Iron-formation have played an important role in the formulation of many of the theories on the origin of the Precambrian iron-formations.

Jan 1, 1968

By W. S. McCain, B. A. Wilcox, A. H. Clauer

The creep and creep-fracture behavior of a Ni-200-2Th0, alloy has been studied over the temperature range 816° to 1038°C and stress range 4000 to 19,000 psi Specimens having their axes either parallel or transverse to the final sheet-rolling direction were tested in air, and the apparent activation energy for creep was found to be 92 kcal per mole, regardless of specinien orientation. The stress dependence 01- the steady-state creep rate, was satisfied by where n depended on orientation; n = 9.7 for rrzaterial transverse to the rolling direction and n = 24.3 for material parallel to the rolling direction. In the latter case, the relation was also valid. The rupture strength of material parallel to the rolling direction was -1.5 times gveater than the transverse rupture strength. Several tests in vacuum revealed that here the creep rate was higher and rupture life lower than for comparable tests in air. THERE is an increased interest today in producing improved dispersion-hardened alloys for high-temperature structural applications. This had led various materials designers to modify existing alloys, such as thoriated nickel. One system that has received considerable attention is based on chromium additions to Ni-ThO2, with the obvious motive of improving the oxidation resistance. Another effect of chromium is that of lowering the stacking-fault energy, y, of nickel. For example, the addition of 30 wt pct Cr decreases y from -225 erg per sq cm for pure nickel1 to -70 erg per sq cm.' This decrease in y could have several effects on the deformation behavior. There is some evidence that cross slip of dislocations around Tho2 particles is a mechanism of tensile3 and creep4 deformation in TD Nickel (Ni + 2 vol pct ThO2) at temperatures below 0.5 the absolute melting point of nickel, T,. A decrease in ? by chromium additions should increase the difficulty of cross slip. Also it has been suggested that the high-temperature (T > 0.5Tm) rate-controlling creep process in "recrystallized" Ni-Tho2 alloys is the climb of edge dislocations over Tho2 particles.5 According to weertman6 a decrease in the stacking-fault energy should decrease the dislocation climb velocity resulting in a decreased steady-state creep rate. Thus, chromium additions to recrystallized Ni-Tho2 alloys would be expected to decrease the creep rate, all other conditions being constant. However, a difficulty arises when the stacking-fault concept is applied to high-temperature creep of dispersion-strengthened metals which are produced on a commercial or semicommercial scale. This occurs because the materials are processed so that they have a high-stored energy of cold work, and the other substructural effects could obscure any influence of stacking-fault energy per se. An example of an alloy with a high stored energy of cold work is TD Nickel bar. This material has a fibrous grain structure (1 I diam by 10 to 15 p long), and the structure is stabilized by the ThO2 particles. Annealing at high temperatures, e.g., 3 hr at 1300°C, causes no recrystallization or grain growth.4 Previous work by the authors4 showed that the high -temperature creep behavior of TD Nickel could not be related to any simple dislocation theory of creep, and this probably was associated with the complex initial structure of the material.

Jan 1, 1968

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

By R. N. Orava

TO the author's knowledge, only one satisfactory high-resolution technique for etch-pitting dislocations in Cu-Zn alloys has been published.' In that account, pits in 70/30 brass single crystals were produced by etching electrolytic ally in a 30 pct orthophosphoric acid bath. Thereafter, observations were made from surface replicas by electron microscopy. The method of pitting and observation permitted the high resolution necessary for the distinction of individual dislocations in arrays of pile-ups. However, no comment was offered concerning the possibility of obtaining pits which are amenable to optical resolution. Moreover, for adequate results, the electrolytic pitting process is invariably preceded by a polishing stage which could obscure the surface features of interest. Consequently, it would be desirable to be able to delineate, by solely chemical means, dislocations which could be detected by both optical and electron metallo-graphic techniques. This was achieved by the simple expedient of modifying two etchants reported by young2 to reveal dislocations on the (100) planes of pure copper. Single crystals of 70/30 a brass, described previously,3 were sectioned to provide a surface parallel to a set of {100) planes, mechanically polished, and subsequently electropolished at 2.4 v in a solution comprised of 2 parts H3PO4, 4 parts ethanol, and 3 parts water. The inclusion of ethanol tended to inhibit nonuniform surface attack. Etch-pitting was effected by a 2 to 3 sec immersion in a 70 pct aqueous solution of HNO3. The samples were then washed in a fast-flowing stream of water, and rinsed further in distilled water, and ethanol, before drying. It is important to note that this reagent should be either used immediately after mixing, or, if allowed to cool, reheated to about 35°C prior to use. No pitting was obtained at room temperature. Typical results are shown in Fig. 1 where (a) is an optical view of the pitted surface and (b) is an electron micrograph of a silicon monoxide replica shadowed with tungsten oxide. The former is characteristic of a somewhat longer etching time (-6 to 8 sec) which varied with bath temperature. Similar pits accrued from a 1/10 aqueous dilution of another of Young's solutions2—2 M FeC1,6H20 and 7.8 M HBr.

Jan 1, 1968

By R. D. Pehlke, J. V. Gluck

A study was made of' the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner's first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry's law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner's well-known expression for the activity coefficient' is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors'-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:''

Jan 1, 1968

By W. D. Robertson, J. -P. Briant, M. Gell

The distribulion of dislocatiorls genevnted during the propagalion of hydrogen-induced cracks in Fe-Si cryslcrls was studied as a funclion of temperature f-110o lo 243°C) and silicorz conlenl (3.1 and 4.2 pct). It zoas found that the clislocntiotl densily and the size of the plctslic zone increased with increasing tempevalnre and decreasing silicon conlent. Furtheruvzove, there was a correlcrtion in the dislocalion patterns formed around cracks that propagated at different tempevattrt-es in cvyslals of diffevent silicon contents such that a 1 pcl itlcverise in silicon content was equivalent to a lemperaluore redziclion of approximately 120°C. The experimenlal YeSnllS were compaved with the results of an elastic-plastic wodel that relates the size of the pluslic .zone to the cvack length, internal pressure, and yield stress. it was found that the clzunges in the dislocctlion cryrays with lemperature and combosition can be e-kplaincd by the lemperatrnre and composilion dependence of the yield stress. An wmtsual feature of this study was the observation of low -temperature noncrystrrllogruphic cracks. PLASTIC relaxation can occur at the edge of a moving crack by the operation of pre-existing dislocation sources or by the creation of new sources in a region of perfect 1attice.l'2 The amount of relaxation in a given crystal depends on the crack velocity and the temperature, and can determine whether a crack propagates in a brittle or a ductile manner.1-3 Tetelman and Robertson4 observed microcracks m Fe-3 pct Si single crystals that formed on (100) planes by the precipitation of hydrogen gas during electrolytic charging at 23°C. The plastic deformation accompanying crack propagation was observed in the form of dislocation etch pits and an extensive analysis has been made of the size, shape, and crystallography of the dislocation arrays5-7 This paper describes the effect of temperature on the plastic deformation generated around hydrogen-induced cracks in Fe-3.1 pct Si and Fe-4.2 pct Si single crystals. The observations are compared with the results of an elastic-plastic model for yielding around a crack containing an internal pressure. 1) EXPERIMENTAL PROCEDURES The composition of the materials used in this study are given in Table I. Single crystals of alloy A and the 4.2 pct Si alloy were grown by the strain-anneal method; crystals of alloy B and the 5.1 pct Si alloy were cut from an ingot grown from the liquid. he ~ingle-cr~stal metallographic specimens had a Cross section of 0.100 by 0.050 in. with a length of at least 3/8 in. Specimens were annealed for 3 hr at

Jan 1, 1968

By A. J. Opinsky

ThE superior performance of nonsag tungsten wire in lamps has been ascribed to the large-grained micro-structure that can be developed in it. The orientations of these large grains have been studied several times; most published data1-' appear to be similar to those plotted in Fig. 1. These new data were obtained by X-ray back-reflection Laue technique from all of the large grains occurring in thirteen different wires that had been heated at the lowest possible temperature for the formation of large grains. Here the wire axis is plotted in terms of the principal directions of the cube. Rosi decided that the preferred orientation of the large crystals could be described by a single ideal orientation, (531), being parallel to the wire axis.' Rieck2,3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Seigle argued that the data suggest that (211) is parallel to the wire axis instead of a single ideal orientation.5 This {211} contains the (531) ideal orientation and would appear to be a more general case. Ahlborn and Wassermann report that their orientation data stretch from ( 110) through (531) to (311) 8 This is part of the locus of (211). All these investigators have determined the orientations of the large grains by back-reflection Laue techniques. They have all obtained essentially similar results. On the other hand, Swalin and Geisler, who obtained their data by neutron diffraction, indicated that the preferred orientation of the large grains in doped wire is (110) .7 These findings cannot presently be reconciled with the pole density data described in the previous paragraph. Rosi1 and Rieck2 have advanced arguments about how their orientations could occur. Nevertheless, the crystallographic link between the (110) (cold-worked) fiber texture and the preferred orientation of the large grains has remained missing. This link can be provided through the concept of coincidence-type boundaries. Such boundaries separate two grains that have a certain number of common lattice sites. Coincidence relationships that result from rotations about low index directions are given by Brandon et a1 .' What is desired is a calculation of those orientations that bear a coincidence relationship with the (110) fibers of the cold-worked matrix. This situation arises in the following fashion. Heating the tungsten wire for a combination of time and temperature falling short of the formation of the nonsag structure yields a structure that is still fibrous in nature and the preferred orientation remains (110). During grain growth, the growing grain is in contact with these fibers. It is hence possible that the entire process may begin by the passage of a coincidence boundary into a (110) fiber. The calculations were carried out analytically and checked graphically. Following Brandon et a1.,8 coincidence relationships from 1 in 5 to 1 in 19 have been considered. The results of the calculations are given in Fig. 2. Of the coincidences examined, some of those occurring upon rotation about ( 110) come closest to the experimental points in Fig. 1. Nineteen of the twenty-three data points in Fig. 1 can be attributed to the ideal orientations A, B, C, and D in Fig. 2. As determined analytically, three crystals lie within 4 deg of point A, four lie within 21/2 deg of point B, eleven lie within 5 deg of point C, and one lies within 1 deg of point D-a total of nineteen. The off-lying points are near the |110| point of the triangle.

Jan 1, 1968