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By Harry L. Brown, James M. Dickinson, Philip E. Armstrong

The elastic stiffness coefficients of niobium have been rneaslrred from -150°C to over 650 C and ave in accord with the anomalous temperature dependence previously observed for Young's modulus. This unusual behavior has been shown to be the result of changes in the relative values of the shear elastic coefficients. The bulk modulus remained essentially constant over the temperature range studied, while changes in the shear coefficients produced a more nearly isotropic behavior as the temperature increased. A number of investigators have reported data on the temperature dependence of Young's modulus of polycrystalline niobium. The values cited for the room-temperature modulus ranged from 0.71 to 1.17 x 10" dynes-cm-' (10.3 to 17.0 x lo6 psi) and in each case the modulus was observed to decrease with increasing temperature. In our recent study,8 both polycrystalline and single-crystal samples of essentially strain-free high-purity niobium showed a Young's modulus whose temperature dependence as well as magnitude was strongly dependent on specimen orientation. This was shown to be the result of changes in the relative magnitude of the two shear moduli, C and C'. Young's modulus of polycrystalline samples with strong [110] textures and Young's modulus of single crystals whose orientations were away from the [loo] actually increased as much as 12 pct between room temperature and 1000°C. While studies on the residual effects of previous fabrication, thermal treatments, and impurity contents will probably resolve the problem of the widely differing Young's modulus values observed in polycrystalline niobium, a more complete description of the elastic properties requires an evaluation of the single-crystal elastic constants. A knowledge of these constants can provide a clearer picture of the nature of the temperature dependence, as well as establish a basis for predicting the modulus behavior of polycrystalline niobium, both in the randomly oriented condition and with various fabrication textures. The effects of residual strains on the elastic behavior then can be separated from orientation effects. EXPERIMENTAL METHOD Thin rod-resonance techniques were used to obtain both the Young's modulus and shear modulus of single-crystal specimens. The determination of these moduli as functions of the crystallographic orientation of the specimen axis provided sufficient information to permit calculation of the single-crystal elastic constants. The necessity for torsional as well as longitudinal measurements led to the design and assembly of a vertical-tube vacuum furnace incorporating probes for the simultaneous determination of both longitudinal

Jan 1, 1967

By D. I. Bardos, F. X. Spiegel, R. K. Malik, Paul A. Beck

Study of the occurrence of elongated ß-Mn phase fields and of their direction of extension in fifteen ternary systems indicates that the ß-,mn phases formed by manganese with other transition elements and with either silicon, germanium, or tin may be considered as electron phases. In these phases the alloying behavior of silicon on the one hand and of germanium and tin on the other shows a significant difference . Formally all observations can be satisfactorily described by attributing to germanium and tin an apparent electron concentration of nine electrons per atom. This behavior may be interpreted by assuming that germanium and tin exclude itinerant electvons because of a strong repulsive potential arising fromthe requirement that their wave junctions be orthogonal to those of- the closed d shells of these atoms. The absence of a d shell in silicon allows this atom to admit itinerant d electrons. The following new ternary phases of unknown structure were identified by means of their X-vay difjraction patterns: (Mn,Co,Si)I , (Mn,Co ,Si)Y, (Mn.Co,Si)Q , (Mn ,Ni ,Si)W , and (Mn, Ti ,Si)A. The X-ray data suggest that these phases have large unit cells and that to some extent they may he related structurally to the 0 phase. The a phase and certain other phases formed by transition elements are characterized by their preferred occurrence at a constant electron concentration. AS a result, these "electron phases" have relation to electron concentration. The tendency of the B phase to form elongated phase fields in ternary systems along the directions of constant electron concentration has been previously demonstrated. The occurrence of an elongated 0-Mn phase field in the ternary system Mn-Co-Si was schematically indicated by Cherkashin et al.l0 The present study includes fifteen ternary systems, each containing in addition to manganese a second transition element from the group Ti, V, Cr, Fe, Co, Ni and one of the nontransition elements silicon, germanium, or tin. In each system the boundaries of the B-Mn phase were determined in the 900°, 950°, or 1000°C isothermal section, the temperature being dictated on the one hand by the requirement of sufficient rates of diffusion to approach equilibrium conditions in reasonably short annealing periods and on the other hand by the need to avoid as much as possible the partial melting of alloys during annealing.

Jan 1, 1967

By S. Floreen

Seven iron alloys ranging from 5 to 12 pct Ni and 5 to 14 pct Cr were studied. All alloys transformed to bcc massive martensites. Tempering increased the strengths , probably because of relief of residual stresses generated by the martensite transformation. The major strengthening mechanism appeared to be solid-solution hardening by nickel and chromium. Studies of the work-hardening behaviw, of the effects of prior austenite grain size, and of the effects of changing strain rate and test temperature gaue results very similar to iron or low-alloy steels. Increasing nickel contents markedly improved the toughness at subzero temperatures. Studies of the flow properties did not, however, indicate the reason for the beneficial effect of nickel on toughness. The marine atmosphere corrosion resistance of the alloys was improved primarily by chromium additions, but increasing nickel contents were also beneficial at low levels of chromium. J\ number of maraging and PH stainless steels are strengthened by precipitation hardening in a low-carbon Fe-Ni-Cr martensite matrix. To some extent the resultant properties of these steels must depend upon the properties of this matrix. The present study therefore was conducted to evaluate the transformation characteristics and mechanical properties of a series of Fe-Ni-Cr martensitic ternary alloys. A limited evaluation of the corrosion resistance of the alloys in marine atmosphere was also made. ALLOY PREPARATION Seven 100-lb air induction melts were prepared using electrolytic iron, nickel, and chromium metal additions. The initial Fe-Ni charge also contained 0.05 wt pct graphite to produce a carbon boil during melt down. After melting of the base charge, the heats were refined with 0.1 wt pct additions of manganese, silicon, aluminum and titanium and poured into cast-iron molds. The ingots were homogenized at 1250°C and uni-directionally hot-rolled to 2-in. plate. They were then homogenized another hour at 1250°C, and unidirection-ally hot-rolled to %-in. plate at a finishing temperature of approximately 1050°C. The compositions of the heats are given in Table I. Two additional heats were prepared as 40-lb vacuum-induction melts using electrolytic iron, nickel, and chromium metals, and commercially pure molybdenum chips. A carbon boil, and 0.1 wt pct additions of aluminum and titanium were again employed, but manganese and silicon were not added. The heats were converted to %-in. plate using the procedure described above. The compositions of these heats are included in Table I.

Jan 1, 1967

By P. N. Nikiforuk, M. C. Zoerb

An analog computer model has been developed of a large, walking dragline. This model permits changes in the configuration of the dragline, or changes in its digging cycle, to be readily investigated on a computer. As a result, it is possible to determine ways of improving the dragline performance without having to carry out many expensive experiments on the actual machine. This model can also be used as a simulator for dragline operator training. INTRODUCTION The movement of large volumes of material is always a costly operation and the increasing trend towards the use of large capacity equipment does not necessarily produce the economy desired. This problem is of particular concern to the mining industry in its open-pit operations where large draglines are used to remove the overburden. Since this operation often forms a very large part of the total cost of open-pit mining it is particularly important that it be kept as economical as possible. This requires that the dragline be operated at its maximum possible productivity. In order to optimize the operation of a dragline it is desirable that a suitable model of the dragline be available for study. Once such a model is available the effects of changes in the configuration of the dragline, or changes in its digging cycle, could be readily investigated on a computer and methods of improving its performance could be determined without having to carry out expensive experiments on the actual machine. Such models would be of use not only to dragline users, but also to the manufacturers of draglines for design purposes. Presumably studies of this type could eventually lead to computer-con trolled stripping operations. As far as can be determined very little work1'2 has been done on the derivation of dragline models. Such models must be derived before work of the nature indicated in the previous paragraph can be carried out. As a small contribution to this field this paper describes work that has been carried out by the senior author during the past few years on the derivation of one such model. This model describes the drag, hoist and swing operations of a 35 cu yd, commercially available, walking dragline. This model was derived for use with an analog computer and can be used either for optimization studies, or for the training of dragline operators. DESCRIPTION OF DRAGLINE General: The particular dragline for which an analog computer model was developed is owned by the Great West Coal Company of Estevan, Saskatchewan. It is a walking dragline and its function is to remove 40

Jan 1, 1967

The Keweenaw Peninsula in the Upper Peninsula of Michigan is plagued with abandoned prospectors' test pits and mine shafts, the result of exploration and operation of mines for over 100 years. The Fort Wilkins State Park in Keweenaw County alone has three open prospectors' pits within its boundaries, protected by wooden fences and maintained by the (Michigan State Conservation Department as a tourist attraction.

Jan 1, 1967

By H. Kahata, I. Iwasaki, Y. Takahasi

A combined process of segregation roasting-flota-tion or magnetic separation was developed to recover nickel from lateritic iron ores and oxidized nickel ores. An ore was mixed with a halide, such as sodium or calcium chloride, and a solid reductant, and roasted, whereby the nickel content was segregated out as discrete metallic particles. Either by magnetic separation, or by flotation using a sulfhydryl collector together with a heavy metal salt as an activator, the metallic nickel could be concentrated, Effects of such variables as the types and amounts of the halide and solid reductant addition and of the roasting conditions were extensively investigated. The concentration results on several types of ores from Japan, the Philippines, and New Caledonia are presented. Laterite is a residual product of rock decay in tropical and subtropical regions, and consists mainly of hydrated oxides of iron and alumina. Those derived from serpentine sometimes become enriched in nickel, cobalt, and chromium contents. Oxidized nickel ores are of the similar origin, but their nickel as well as silica contents are higher due to gamierite-type silicates. Apparently, nickel enrichment is more pronounced in the transition region between the surface layer of iron laterite and the underlying serpentine. Iron laterites often contain over 50% iron, and their reserve is reported to exceed 22 billion tons, corresponding approximately to 20% of the world iron ore reserve.1 It is readily apparent, therefore, why the iron laterites have attracted much attention of the steel industry as a potential source of iron ores. Numerous attempts to remove nickel and chromium as byproducts, have been reported in literature.' Worldwide discoveries of high-grade iron ore deposits in recent years have inevitably lessened the interests in iron laterites. However, in view of the tremendous potential for their gross value and supplies of nickel, cobalt, chromium, and alumina along with iron, the problem remains as a challenge. Much of the chromium in laterites is present in the form of relatively coarse particles of chromite, and various classification methods have successfully been applied for its removal.2,3 The nickel, however, is intimately associated with limonite, and ordinary concentration techniques are totally ineffective. Much attention has, therefore, been given to hydro-metallurgical or pyrometallurgical means. Yet, all the known processes appear to have limitations either economically or for the use of products as iron raw materials due to a high residual content of nickel. Some attempts have been made to pre-roast laterites or oxidized nickel ores, particularly with sulfidizing agents, and to remove nickel either by magnetic separation,' or by flotation.4 It is apparent that any such concentration process would require grain growth of nickel during roasting for effective separation. Oxidized copper ores are reported to be concentrated by the segregation roasting-flotation process,5 in which the ores are roasted with a chloridizing agent and a carbonaceous reductant in order to promote the growth of metallic copper through repeated cycles of copper chloride volatilization and its reduction on the solid reductant surfaces. Examination of a vapor pressure-temperature diagram of various metal chlorides indicates that a separation of nickel from iron may be effected by a similar process. In fact, the segregation roasting of laterites was reported to increase the extraction of nickel by the ammonia leach process, as compared to the ordinary reduction roasting.6 In the present article some of the preliminary experimental results of the segregation roasting, followed by either flotation or magnetic separation, on laterites and oxidized nickel ores are reported. The effects of various parameters in the roasting as well as in the concentration steps are discussed. MATERIALS AND METHODS An oxidized nickel ore from Thio, New Caledonia, and three laterites from Homonhon, the Philippines, Wakasa and Miyagawa, Japan, were selected for the

Jan 1, 1967

By R. A. Friedel

THE IMPORTANCE of infrared and ultraviolet-visible spectrometry in studies of the structure of coal and similar substances is described. Special experimental techniques have been developed for these studies. Thin sections of coal are preferred, but halide pellets are easier to prepare. Information obtained from infrared spectra on chemical functional groups has been discussed; the importance of both intensities and wavelengths of absorption bands has been emphasized. Functional groups assigned include aliphatic and aromatic CH, methylene and methyl groups, hydrogen-bonded hydroxyls, hydrogen-bonded and chelated carbonyls, phenolic structures, minerals, and aromatic structures that are benzenoid or polynuclear. Infrared studies of structures of coal extracts, distillates, and reaction products of various processes, both chemical and physical, are discussed. Coallike infrared spectra of chars of model compounds have been utilized extensively in studies of coal structure. Ultraviolet-visible absorption spectra of coals show a lack of fine structure and low spectral intensities. These results have been applied to the questions of the chemical and physical structure of coal, particularly the question of polynuclear aromaticity of coals. The color of coal is also treated. The physical-chemical origin of the color of coal may be due to free radicals, as interesting correlations of ultraviolet-visible spectra with electron paramagnetic resonance have been obtained. The optical color of coal has been explained and simulation of the color changes observed in thin sections has been carried out, The spectra and structure of coal derivatives and other carbonaceous materials are also discussed. Possible sources of error in absorption spectral measurements are pointed out. Limited measurements of the ultraviolet-visible reflectance spectra of coal are described.

Jan 1, 1967

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß'-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,' alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0' phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967

By Katherine Harding

Basic concepts of matrix algebra and manipulations of matrices are presented in such a way that little competence in mathematics is required. Examples are always included to illustrate concepts and techniques. The paper is divided into six sections. The first four sections are devoted to some of the more basic concepts of matrix algebra, whereas the last two sections are concerned with specific applications.

Jan 1, 1967

By Donald Ofte

LIQUIDUS temperatures of molten alloys were measured in an oscillating-cup viscosimeter by observing the abrupt increase in the alloy viscosity when the apparatus was cooled below the alloy liquidus temperature. The liquidus transformation can be an elusive thermal effect in an alloy system where a small amount of material is involved in a low-enthalpy liquidus reaction, or where other unfavorable physical conditions interfere. Using the viscosity technique, liquidus temperatures were measured in binary alloys of plutonium with cerium, gallium, and iron, as well as ternary Pu-Ce-Co alloys. The previously described oscillating-cup viscosimeter1 is a torsion pendulum consisting of a right circular, cylindrical tantalum cup fitted to a rigid shaft which, in turn, is suspended by a torsion fiber in a highvacuum system. When the torsion pendulum is placed in oscillation the viscosity of the liquid contained in the cup is a function of both the decay of the oscillation caused by the viscous drag of the liquid contained in the sealed tantalum cup, and the period of the oscillation. The period is measured by a photo-electrically operated timer to the nearest thousandth of a second. Prior to each measurement, the apparatus is held at temperature between 5 and 18 hr to assure thermal equilibrium throughout the 8 to 10-cc alloy sample. When the cup, filled with a liquid metal, is oscillating. only a very thin outer layer of the fluid is in motion. This moving annulus represents the liquid's contribution to the moment of inertia of the torsion pendulum. When the viscosity increases, more liquid is placed in motion, and the slight increase in the moment of inertia causes a corresponding increase in the period of oscillation.

Jan 1, 1967

By J. W. Spretnak, V. Kandarpa, G. W. Powell, R. A. Erickson

Neutron-diffraction pattens were obtained at room temperature from two austenitic manganese steels, oxc wth n carbon content of 1.23 zct PC/ and the olher 0.63 wt pct. Analysis of the data showed that the curOan atols (ions) occupy tile octaheadral site. any of the cavbon is in the tetahedral site, tile concentration is too strzall lo be detecled by tzeulr-on d$facton. AS part of a long-range investigation of eutectoid decomposition, a study of the structure of austenite has been undertaken in order to characterize as best as possible the parent phase in the Fe-C system. Austenite is a solid solution of carbon atoms in fcc iron, the carbon atoms being located in interstitial positions. Of the two kinds of interstitial sites, octahedral (0, +, +) and tetrahedral (4, a, $), in this lattice, the larger octahedral sites are usually considered as the probable position of carbon. The strain energy involved in pytting a neutral carbon atom (covalent di; ameter 1.54)' into a tetrahedral site (diameter 0.56A) is considerably greater than that associated with p2tting carbon into the octahedral site (diameter 1.08A). Dayal and arkeen' observed the migration of carbon in iron under the influence of an electric field indicating tha tye carbon is ionized. pe ionic radius of C'4 is 0.15A and that of C" is 0.29. Consequently, it is conceivable that carbon ions could occupy the tetrahedral sites if one considers only the strain energy. Size considerations alone do not provide a complete explanation for the formation of the interstitial solid solutions, however. because metals such as copper, zinc, and cadmium do not appear to form interstitial solid solutions in spite of their large interstitial sites. Evidence which suggests partial ioni-zation of the carbon in austenite has also been obtained by Speiser, Spretnak, and alor who derived formu- lae relating the observed change in lattice parameter to the effective diameter of the solute atom. Assuming the carbon occupies the octahedral site. they computed the effective diameter of carbon to be 1.33A whereas the covalent diameter is 1.54A. petch5 concluded from powder X-ray diffraction experiments that carbon atoms occupy the octahedral sites. His conclusion was based on the general trend observed in the intensity of the diffraction lines as the carbon content of the austenite was increased. However, the major difficulty associated with application of X-ray diffraction to this particular problem is the relatively poor scattering power of carbon. Williamson and smallman' utilized X-ray diffraction to study the line broadening caused by the strain field about carbon atoms inferrite: these investigators concluded that at least 85 pct of the carbon in ferrite occupies the octahedral (0: 3, B) site rather than the larger

Jan 1, 1967

By P. Wynblatt, J. E. Dorn

The effect of strain rate, temperature, and interstitial impurity concentration on the flow stress was investigated in a poly crystalline Fe-2 pct Mn alloy. The temperature dependence of the flow stress was found to be independent of the interstitial impurity concentration, removal of interstitials merely decreasing the atherma1 stress level. Below 160%, the large temperature dependence of the flow stress was interpreted in terms of the Dorn-Rajnak theory of the Peierls mechanism of plastic deformation. Above 160"K, some other thermally activated intrinsic meckanisln seems to be operating. The strong temperature dependence of the flow stress of bcc iron at low temperatures has been studied by numerous investigators and interpreted in terms of several different thermally activated dislocation mechanisms. The following mechanisms have been proposed: a) interaction of dislocations with interstitial impurity atoms1 or with solute atoms in general; b) interaction of dislocations with clusters of impurity atoms;3 c) resistance to the motion of dislocations due to jogs on screw dislocations;* d) resistance to the motion of dislocations due to the Snoeck effect;' and e) interaction of dislocations with the intrinsic resistance of the bcc lattice or Peierls "hills". In previous work: it was found that the plastic behavior of polycrystalline iron containing 2 wt pct Mn (and 100 ppm C + N) is in good agreement with predictions based on the Peierls mechanismlo from 77" to 160°K whereas from 160" to about 370°K another as yet unidentified thermally activated mechanism is operative. The purpose of the present investigation was to determine the effect of interstitial impurities on the temperature dependence of the flow stress, by purifying the previously investigated alloy with respect to interstitial impurities. The investigation revealed that removal of the interstitial impurities to a level that eliminated Cottrell locking and the Portevin-LeChatelier effect (i.e., serrations in the stress-strain curve due to dynamic strain aging) affects neither the strong temperature dependence of the flow stress at low temperatures nor the general characteristics of the higher-temperature behavior. Such purification, however, lowered the athermal yield stress. I) EXPERIMENTAL PROCEDURE AND RESULTS The material used in this investigation consisted of an Fe-2 wt pct Mn alloy having the following additional elements present: 0.004 pct C, 0.006 pct N, 0.05 pct 0, 0.004 pct S, 0.003 pct P, and 0.001 pct Si. This was the same material as that studied in the previous investigation and will henceforth be referred to as the "impure material". The as received -jr by 2 in. hot-rolled bars were cold-rolled to 0.08-in. thickness, recrys-tallized under argon for 30 min at 80O0C, and further cold-rolled to 0.053-in. thickness. Flat tensile specimens 3 in. wide having a 1.625-in.-long gage section were machined from the sheet and then purified. The first stage of purification consisted of holding the specimens at 850°C for 24 hr in a stream of hydrogen saturated with water vapor at room temperature. Material prepared in this fashion will subsequently be referred to as "wet hydrogen purified material". It has been estimated that this type of treatment reduces the carbon content of iron to less than 5 ppm.' The second stage of purification consisted of holding the specimens in a closed system through which hydrogen was circulated past the heated specimens as well as a zirconium hydride getter. The specimens were held at 850°C and the getter at 800°C. The process was continued for 212 hr. The starting material for this process was wet hydrogen purified material. Material prepared in this manner will be referred to as "ZrHz purified material". The technique used was substantially the same as that described by Stein et al.' who have shown that the carbon level at the end of the process is reduced to about 5 parts per billion. The mean grain size of the three materials was found to be -60 C( for the impure material and -160p for the wet hydrogen and ZrHz purified materials. All tensile testing was carried out on an Instron Testing Machine either in controlled-temperature baths or at fixed-point baths such as boiling liquid nitrogen, and so forth. When fixed points were used the temperature was kept constant to better than *1°C whereas in all other tests the temperature variation was less than *2°C. Test of Purity. It was not possible to determine the purity achieved at each stage of the purification because the resulting level of interstitial impurities was near or below the limit of sensitivity of standard analytical techniques. It was possible, however, to obtain a qualitative measure of the extent of purification from the appearance of the stress-strain curves for the three materials. Fig. 1 shows the stress-strain curves for the three different materials tested at 300°K. It can be seen that the effect of wet hydrogen

Jan 1, 1967

By David E. Nicholson

In a Bureau of Mines investigation of the dynamic compaction of mine hydraulic backfills, two basic forms of mechanical vibration inducers were used and compared for effectiveness of compaction. Internal compaction, using concrete probe vibrators of various sizes, and external compaction, using plate vibrators} were studied and evaluated for use in underground stopes. An aluminum plate, which was light and displaced sufficient volume to remain afloat in fluid fill, and a steel plate were both used in the external compaction tests. Efficiency of compaction was better in studies conducted with internal probe vibrators. Tests were conducted in an underground backfilled stope with three different-sized probe vibrators (2-, 4-, and 6-inch-diameter) to determine an approximate area of influence. Results showed the areas of influence to be approximately 3, 4, and 5 feet in diameter, respectively, for the three different probes. Physical properties of hydraulic slurries were determined; preferred grain-size distributions, water exudation properties, and water contents of hydraulic slurries are reported. The best compaction results were obtained with moderately well-graded, fully saturated backfills, with slow rates of water exudation, which were capable of remaining in a semifluid state during the compaction process.

Jan 1, 1967

By P. M. Robinson, J. S. LI. Leach

The heats of solution oj' indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az'erage deviation from the Kopp-l\'ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.' The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623'K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.' The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By F. A. Skirvin

Purification techniques were investigated for removing low-level metallic impurities from tungsten hexachloride. These techniques included distillation) fused-salt scrubbing) zone refining) and adsorption. Fractional distillation of tungsten hexachloride was found to be an effective purification method. The impurity levels of molybdenum) iron) nickel) copper) magnesium) and manganese were reduced to provide a tungsten halide sample which contained a total of less than 10 ppm detectable metallic impurities. Purification by fused-salt scrubbing of tungsten hexachloride in a lithium chloride-potassium chloride eutectic produced a hexachloride product which was of approximately the same quality as that obtained by distillation. Zone refining and adsorption did not appear to be as effective as distillation or fused-salt scrubbing.

Jan 1, 1967

By Harry Elkin

Control of coal dust has long been an important aspect in the conventional mining of coal; the main reasons being from a health and disaster standpoint. With the advent, of mechanized longwall mining, the control of dust has required more attention due to the high extraction rate common to most longwall systems. The purpose of this paper will be to describe the dust abatement activities of the longwall operation at Sunnyside. Kaiser-Steel Corporation has three mires located at Sunnyside, Utah, with a total production averaging 6,800 tons of clean coal per day. Of this 6,800 tons, 71 % is mined with continuous miners, the remaining 29% coming from one longwall unit located in No. 3 Mine. Our first longwall panel was started in November, 1961. In October, 1966, we started mining our seventh panel. The present panel is located in the Upper Sunnyside Seam which averages five feet in thickness, but does get as low as 51 inches. The seam pitches 5.5% in this vicinity. The roof is generally good and is comprised of 10 inches of shale cap rocs overlain with sandy shale and sandstone. The floor is sandy shale and is quite undulating in nature. The present panel is 3,800 feet in length with a face of 670 feet. The major equipment employed on our longwall unit is a 125 H.F. Anderton Shearer-Loader, British Jeffrey Diamond armored conveyors and a Dowty self-advancing-roof support system. The Anderton Shearer in use on our longwall unit has a 60" diameter x 27" cutting drum. During the shearing cycle, it traverses the face at 20 feet per minute with a cutting rate of 7.5 tons/minute.

Jan 1, 1967

By H. K. Birnbaum, H. B. Aaron

he authors suggest that a number of the types of yield phenomena which have been observed in high-purity fcc metals are due to dislocation interactions bccurring at the surface of the crystals rather than due to volume effects. Since rather different inter-pretationS2,7,12,14,15,21-23 of these effects have been suggested, it is of some importance to ascertain the role of the surface in these yield phenomena. It should be first noted that the high-purity fcc metals appear to exhibit several distinct types of yield phenomena. The "unloading yield point" which is observed on reloading the specimen after removing the applied load has been found to be independent of the time of holding in the unloaded condition. If however the specimen is aged while under load and re-tested without removing the load, a yield point is observed which does depend on the aging time and tem-perature. Feng and Kramer suggest that the removal of the unloading yield point on removing sufficient material from the surface of the specimen indicates that the effect is associated with dislocation interactions at the specimen surface. Their observations are counter to those of Haasen and Kelly5 and Birnbaum.12 Since the unloading yield points are extremely small (-2 pct of the flow stress) the results of the surface removal will depend on whether the material is removed uniformly over the gage length. The introduction of small etch pits or the removal of more material from one portion of the specimen than from another will result in preferential yielding and obliteration of the yield point. With the normal electropolishing techniques it would be difficult to avoid these effects. The data obtained by Aaron and Birnbaum, Fig. 10, on aluminum polycrystalline specimens indicate that, although the unloading yield point and the strain-aging yield point are not simply additive, a time- and temperature-dependent yield point is observed under conditions where no creep is observed. This does not agree with the results of Feng and Kramer but does agree with the results on copper15 and gold.7~23 The source of the discrepancy may be the procedure used by Feng and Kramer to correct their time-dependent yield points for the effect of creep. Since the strain-aging yield point is not independent of the pre-aging strain rate, Fig. 11, the effects of creep cannot

Jan 1, 1967

By G. G. Campbell

The Bureau of Mines in cooperation with Quaker State Refining Corp. conducted two underground-combustion oil-recovery experiments in the Venango Second sandstone in the Reno pool, Foster-Rena-Oil City field, Sugar Creek Township) Venango County, Pa.) to determine the applicability of the process for reservoirs producing Pennsylvania-grade paraffin-base crude oil. Tests were terminated when analyses of produced gas showed that a self-sustaining combustion front did not exist. It was thought that insufficient fuel had been deposited in the formation. Laboratory retort tests made after the second field test was concluded showed that crude oil from the Reno area would deposit enough fuel to support combustion if air flux, temperature, and time were maintained within defined limits.

Jan 1, 1967

By David W. James

DURING a recent investigation of the transition from a planar to a nonplanar solid/liquid interface for the systems H20-NH4F and 0-AIR,' an apparatus was developed which enabled the morphology of the ice-water interface to be examined during the transition. The slightly curved interface was viewed at a glancing angle with a Bausch and Lomb X30 stereomicro-scope. The interface was obliquely illuminated by a polarized light source. It was thus possible to differentiate between small projections or depressions at the interface, both by a shadowing effect and by the way in which they distorted the colored interference fringes across a particular crystal surface. Many attempts were made to photograph the various stages of interface breakdown. Unfortunately, the limited depth of focus of the microscope rendered the system unsuitable for photographic recording. Visual examination, however, was facilitated by continuous adjustment of the microscope focus control. The following observations of the interface transition were recorded for dilute solutions of ammonium fluoride in water. They are compared with iller's postulated morphologies shown in Fig. 1. i) The initial departure from planarity was characterized by the appearance of a large number of small depressions or "pores" in the interface. ii) The pores were arranged in wavy rows all lying roughly in the same direction within a particular grain. iii) The pores did not appear to form near to grain boundaries. iv) The pores appeared in certain grains before others. v) The transition from the pore structure to the elongated cell structure, Fig. l(d), was difficult to follow. It occurred quite rapidly and no truly irregular cell structure, Fig. l(c), was noticed. vi) The elongated cells gradually became more uniform in size and shape, with straight cell boundaries. They remained elongated, however, and no regular hexagonal cells were observed, cf. Fig. l(e). Several conclusions may be drawn from these observations. Firstly, the appearance of a poxed or, more accurately, a pore structure can be used as a criterion for the onset of constitutional supercooling. Care should, of course, be taken to distinguish between the true pore structure and artifacts caused by splashed-back liquid, particles of oxide, or inefficient decantation of liquid retained between cell boundaries, as described by Spittle et al? Secondly, and contrary to the suggestions of Tiller el l., it seems that interfacial perturbations are characterized not by curved projections but by small depressions or pores. A recent independent investigation by Biloni, Bolling, and cole5 reported in this issue indicates that the depressions might be explained in terms of dislocations intersecting the solid/liquid interface. It is possible that the dislocation concentration is reduced in the vicinity of grain boundaries. This would then explain the grain boundary depleted areas noted in (iii) above. This work was partially supported by the Air Force Office of Scientific Research, Contract No. AF 49-(638)-1029.

Jan 1, 1967

By K. E. Manchester, C. B. Sibley

The feasibility of doping silicon to produce device structres by directly implanting impurity atoms has been demonstrated. Both phosphors and boron ions have been successfully implanted in silicon to produce electrical junctions. Junctions as deep as 1.2 p have been produced by phosphorus ions having energies the order of 80 kev. An electromagnetic separator has been used to controllably produce uniform, large-area implantations for evaluation experimentation. Correlations between junclion depths and ion energies huve been obtained. Orientation effects have been observed and it has been found that the (110) direction is the easy direction for implanting. Monitoring of thermal treatments oj implanted substrates by sheet-resistance measurement indicates a very mild thermal anneal removes most of the damage done during the implantation. These indications are further substantiated by reverse-current measurements of j,inctions Produced by implantation. Electrical characteristics of implanted junctions are compared with those of diffused junctions. We have been interi n the interaction of energetic ions in the III-V groups, in particular boron and phosphorus, with single-crystal silicon to produce type conversion for possible device use. A number of investigators, a few of whom are avies, Kornelson,3 and so forth, have reported on penetration of energetic ions into both amorphous and crystalline solids. While most work has been done with ions of the rare gas and alkali metal groups, some work has been reported by ing, erber,' and others6 in which ions of the 111-V groups have been implanted in single-crystal silicon. A large amount of this work has been done with ion energies in the 100-kev to 1.5-Mev range. An excellent review article has been written by caldin. We have concentrated on ion energies which are in the 10 to 80 kev range, with which over 1500 implanted junctions such as the one shown in Fig. 1 have been produced in silicon substrates with both phosphorus and boron ions. Fig. 1 is a 3-deg angle lap in which the n type area produced by 66 kev P is delineated and the junction is 9500A below the surface. EXPERIMENTAL Implantations reported in this paper were made with the ion source adjusted to produce ion currents in the range of 1 to 2 pa with accelerating voltages varied from 10 to 40 kv. When using doubly charged ions this produced 10 to 80 kev ions. This allowed substrate temperatures to remain below 100°C. Sam- ple movement resulted in beam impingement angle variation of 7 deg from the normal to the substrate surface. Substrate resistivities have been varied through the range of 0.001 to 500 ohm-cm and specimens oriented in three directions, (110), (Ill), and (loo), within 12 deg. RESULTS For the purpose of this paper, discussion of results will be limited to phosphorus implantations with mention of results for boron-implanted silicon. Similar results have been obtained for boron and will be reported at a later date. In Figs. 2, 3, and 4 depth penetration is shown

Jan 1, 1967