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By H. J. Wogner

STORAGE of natural gas in underground reservoirs is one of the most important developments in the natural gas industry in recent years. However, it is only when we consider this development together with proved fuel reserves, the know-how of the fuel technologist, and the possibility of making manufactured gas available over large areas, that we begin to appreciate fully the impact that underground storage of gas may have on the future growth and development of large areas in the United States. During the past winter, shortages of natural gas in the industrial East were given wide publicity and domestic consumers were requested to reduce their requirements to a minimum, so that war plants might have sufficient gas to continue operations. Curtailments would have been more drastic except for the fact that large volumes of natural gas had previously been stored in underground reservoirs. Storage of natural gas in depleted or partly depleted gas or oil sands is not new, having originally been tried, as far as I know, about 1915. About five or ten years later an attempt was made to store manufactured gas in a depleted gas sand. This proved unsuccessful at first because the gas was not properly cleaned and the impurities plugged the pores in the sand.

Jan 1, 1945

By J. B. Cheatham

Applications of the mathematical theory of plasticity promises to lead to the solution of many drilling and rock mechanics problems. ,Because of mathematical considerations, the inelastic behavior of rock has frequently been represented by a perfectly plastic model in conjunction with a yield criteria of the Coulomb or Mohr type. The totality of all stress states for which a solid ceases to behave elastically can be represented as a limit surface in stress space. ,Probing of such limit surfaces indicates details of strain hardening which are not provided by the standard triaxial testing procedure. Probing tests of the limit surfaces have been performed on Cardova Cream limestone to provide data for extending plasticity theory to cover situations in which consolidation and strain hardening are present. Test results indicate that this highly porous limestone undergoes a permanent volume decrease when it is subjected to hydrostatic pressures in excess of 3,500 psi. A virgin sample tested under a confining pressure of 1,500 psi has a yield strength of 1,700 psi; however, if the sample is subjected to a consolidation pressure of 5,000 psi, before testing at 1,500 psi, the yield strength is raised to 2,300 psi. Thus, both consolidation and strain hardening are important considerations in describing the mechanical behavior of this limestone. Tests conducted with the axis of the core having different orientations indicate that this rock is also anisotropic. Portions of the initial and subsequent limit surfaces are determined for samples loaded either perpendicular or parallel to the bedding planes. INTRODUCTION Previous experimental work in rock mechanics indicates that no mathematically tractable constitutive theory is inclusive enough to describe the mechanical behavior exhibited by all types of rocks under all conditions of stress and temperature. Indeed, the type of deformation encountered in a single type of rock is known to depend upon the stress and temperature conditions in the rock during deformation.l-5 Certain rocks and minerals, notably those minerals composed of ionic salts, have been shown to exhibit plastic deformation when tested under conditions of high confining pressure.2 Since the mathematical theory of plasticity provides simplifications over the theory of elasticity in certain types of problems, such as those in which limit analysis can be applied, it is of interest to know under what conditions plasticity theory may be applied to rock mechanics problems. The following factors determine the nature of the deformation a particular specimen will undergo: (1) the microscopic structure of the rock, i.e., the structure visible under an optical microscope, including number of phases, porosity, distribution of phases, (2) the mineralogical structure of the solid phases, (3) the conditions of stress and the rate of change of stress and (4) the temperature. Extensive experiments on Yule marble, Carthage marble, Solenhofen limestone and other calcerous rocks indicate that these relatively nonporous rocks deform plastically under certain conditions of loading, and creep under other conditions of loading.l-3 This study is concerned with the behavior of Cordova Cream limestone (Austin chalk) which is also composed almost entirely of calcite and thus has the same mineralogical composition but, because of a rather large porosity, it possesses a different microscopic structure. This investigation was undertaken to learn if Cordova Cream limestone deforms plastically despite the embrittling effect of the pore spaces, and to provide data which can be used to determine whether the mathematical theory of plasticity can describe the mechanical behavior of Cordova Cream limestone. A brief discussion is given of some of the underlying principles of plasticity theory concerning stress space and limit surfaces. Strain hardening is defined and a discussion is given of how the mechanical behavior of a material can depend on the previous history of the loading. This is followed by a description of the experimental procedures

By B. F. Decker, J. H. Keeler, W. R. Hibbard

Textures of hot-rolled, of cold-rolled, and of cold-rolled and annealed zirconium sheets were determined by use of an X-ray spectrogoniometer. All textures showed a tilt of the basal planes 240" from the rolling plane about the rolling direction. Deformation textures showed the [1010] direction to be approximately in the rolling direction. After recrystalliza-tion, the 111201 direction was approximately in the rolling direction. This texture was sharpened by annealing above the allotropic transformation. Textures of sheet produced by alternately cold rolling and then annealing were less strongly oriented than sheets that underwent severe deformation without intermediate anneals. THIS study of the deformation and annealing textures of high purity zirconium was carried out to supplement an investigation of zirconium and zirconium-base alloys. The spectrogoniometer method of pole figure determination was used and yielded more detailed and precise information than the photographic techniques used by previous investigators. Earlier investigations of the rolling textures of hexagonal metals titanium,1,2 beryllium," and zirconiumL having a c/a ratio slightly less than 1.6 disclosed a rotation of the basal planes from the rolling plane about the rolling direction so that the basal poles were inclined toward the transverse direction, and with one exception,& the [1010] direction was found parallel to the rolling direction. Similarly, hot rolling produced a spread of the basal poles in the transverse direction,2,3,5 With the [1010] direction parallel to the rolling direction. The textures of these metals after recrystallization differ somewhat from each other although still exhibiting the transverse rotation of the basal poles about the rolling direction. Zirconium" was found to have the [1120] direction in the rolling direction, beryllium" continued to have the [1010] direction in the rolling direction, and titanium' was shown to have the [1010] direction in the rolling direction (the cold-rolling texture) when annealed at 1000°F, changing to the [1120] direction in the rolling direction when annealed at 1500°F. It was suggested2 that the titanium retains the deformation texture after re-crystallization, and preferred grain growth at higher temperatures produces the second texture. Annealing above the allotropic transformation temperature did not appreciably change the high temperature recrystallization texture for titanium.' Coarsegrained zirconium showed more spread" in the transformation texture than in the recrystallization texture. The material used in this investigation was crystal-bar zirconium prepared by the iodide process. The major impurity was hafnium which was less than 0.3 pct. The composition obtained by spectro-graphic analysis is given in Table I. The hot-rolled specimen was prepared from a 50-g button of zirconium arc-melted in a water-cooled crucible under an argon atmosphere. This button was enclosed in a welded sheath of soft iron and the ensemble was rolled at 825°C. After each pass the sheath was put back into the furnace to allow it to return to the desired temperature. The zirconium ingot was reduced in this manner to a thickness of about 0.035 in., a reduction of approximately 90 pct. The sheet after removal from the sheath was alternately polished and etched to a thickness of 0.001 in. Cold-rolled specimens were prepared from crystal bar by a series of reductions of approximately 0.010 in. until the sheet reached a thickness of 0.010 in. after which it was cold-rolled to 0.001 in. thickness between sheets of alloy steel. The total cold reduction amounted to about 99.8 pct. Specimens were annealed in an evacuated Vycor or quartz tube. The transmission pole figures were obtained by the quantitative method of Decker, Asp, and Harker6 modified by Geisler7 using an X-ray spectrogoniometer with Cu Ka radiation. Unless otherwise specified all four quadrants were examined with 5" increments along the radius of the pole figure. Absorption corrections were made for changes in length of the X-ray path through the sample as inclination of the

Jan 1, 1954

By H. R. Hose

The total crude fluorspar reserves in Western Europe, including the USSR and the Soviet sphere, Thetotalare estimated to exceed 17 million metric tons. The total fluorspar production in 1951 in Western Europe, excluding the USSR and Soviet sphere, amounted to 371,109 metric tons. The chief fluorspar-producing countries in Europe, excluding Russia and the Soviet sphere, are France, Western Germany, Italy, Spain, and the United Kingdom. TOTAL crude fluorspar reserves in western Europe, containing more than 35 pct CaF2, are estimated at 12 million metric tons, while reserves in the USSR and Soviet sphere may exceed 5 million metric tons. The bulk of these reserves are concentrated in the USSR, Spain, United Kingdom, Western Germany, and Italy. Since published estimates of the tonnages of individual mines and explored deposits are not available for most countries in Europe, the estimates given in Table I for individual countries are necessarily approximate, as they have been compiled from various sources and modified and combined according to the author's judgment. The majority of fluorspar deposits in Europe belong to the late Paleozoic metallogenetic epochs and have been found within or along the borders of the Hercynian massifs. Deposits in the Central and Esterel massifs of France, those of Western and Eastern Germany, Sardinia, the Catalonian coastal range and the Sierra de los Santos in Spain, and those of Devonshire and Cornwall belong to the Hercynian metallogenetic epochs. The deposits in southern Norway and Sweden belong to the middle Paleozoic or later, those of northern England to the late Paleozoic or later, those of northern Spain and Greece to the late Mesozoic, and those of northern and probably central Italy and Switzerland to the early Tertiary. Fluorspar occurs typically in veins, lenses, and stringers, but also in bedded replacement deposits and pockets, and may be colorless to white, yellow, green, pink, brown, blue, or purple to almost black. Except for the colorless variety, the only kind which can be used for the optical industry, the color of the fluorspar does not affect its ultimate use. Crystalline cubic or octahedral fluorite of CaF2 composition, with 48.9 pct fluorine and 51.1 pct calcium, has a specific gravity of 3.18. The ore in place, however, usually averages 3.0 metric tons per cubic meter owing to the quantity of other minerals asso- ciated with the fluorspar in the veins and the physical state of the fluorspar, which may vary from sugary to massive crystalline or microscopic inter-growths with barite or quartz. Barite of 4.5 sp gr, quartz of 2.66 sp gr, and chert and calcite are commonly associated with fluorspar. Other minerals usually present in lesser amounts are celestite, wad, silver, lead, zinc, copper, iron, and uranium minerals. In some cavity fillings the rhythmic deposition of the fluorspar, barite, and quartz into successive crusts may make it possible to handpick the crude ore on belts or to separate the fluorspar from other minerals while the actual mining is carried on. Where metallurgical grade lump spar is required for foundries, separation of quartz and barite may be made also by jigs and heavy media, and in some mines the lead and zinc sulphides may be separated and recovered by vibrating tables. However, except in the case of unusually high grade deposits, acid grade fluorspar is obtained by flotation. By this process fluorspar deposits grading down to 35 pct CaF2 in the crude ore can be worked at a profit when fluorspar, lead, zinc, and silver prices are high, as the sulphides of these ores can be separated from the fluorspar by flotation and concentrated.

Jan 1, 1956

By M. L. Hammond, G. M. Bowers

Silicon dioxide films have been prepared on silicon wafers by the oxidation of SiH, near 400°C. Results previously reported by Goldsmith and Kern7 have been qualitatively corrobovated using a system of different geometry, and significantly greater deposition rates have been achieved. The deposition rate is independent of thickness and nearly independent of the O2/SiH, ratio over a wide range; however, the rate is strongly temperature-dependent. The structure of the deposit depends upon the cleanliness of the substrate, and the electrical field strength of the deposited oxide depends upon the nature of the electrodes. MULTILEVEL interconnects in integrated circuits using aluminum metallization require an insulator that can be deposited at low temperature. Because the A1-Si eutectic is only 577°C, the maximum deposition temperature must be below about 500°C to prevent reaction of the aluminum with the silicon and with other materials in the integrated circuit. Many methods of depositing insulating films of SiO, and other dielectrics have been reported'-6 but the technique described by Goldsmith and Kern7 offers the simplest method of preparing SiO, films. The technique involves the reaction of SiH, and 0, to form SiO, films in the 300" to 500°C temperature range. Previous work using this gas system has been reported8 and the initial development work at Philco Microelectronics was done at the East Coast R&D Laboratories. 9 This paper corroborates some of the results of Goldsmith and Kern,7 shows that much higher deposition rates can be obtained than previously reported, and presents some observations on the structure of deposited SiO, films. EXPERIMENTAL CONDITIONS Fig. 1 is a schematic drawing of the apparatus used in this study. It differs from that of Goldsmith and Kern in that 1) the gases are mixed before they enter the reaction chamber, 2) there is no fritted glass diffuser, and 3) the wafers are stationary during deposition. The control thermocouple was in a well located 0.06-in. from the substrate, and three gas supplies were used: 1 pct SiH4 in N 2, O 2, and N 2. Water vapor must be excluded from the plumbing to prevent the formation of colloidal SiO, and the SiH4 must be diluted with an inert gas because SiH4-0, mixtures are extremely flammable above about 4 pct SiH The wafer temperature was determined by attaching a thermocouple to a test wafer and the temperature was maintained to +5 C. The conditions used in this investigation are listed in Table I. The temperature range was chosen for compatibility with the A1-Si system. The volume ratio of 0, to SiH4 is the actual volume of 0, delivered to that of SiH4, taking into account the initial dilution of the SiH4. This ratio, which was used by Goldsmith and Kern,7 is a useful indicator of the experimental conditions. The active/inactive ratio is the ratio of the volume of active gases, SiH4 and O2, delivered to the volume of dilution gas. The active/inactive ratio is an important parameter to specify for deposition rate determinations since it determines the amounts of reactants that arrive at the sample per unit time. Fairly high dilution ratios were necessary to achieve uniform deposits of SiO,. Most of the process characterizations were performed on the polished (111) face of 3 to 5 ohm-cm, n-type silicon wafers which were 0.009 in. thick; but the data approximately apply to deposition of SiO, on thin films of aluminum. It is difficult to obtain accurate deposition rate data over aluminum films because of coarsening the aluminum surface during exposure to 300" to 400°C. The deposited SiO, film fol-

Jan 1, 1969

By D. de Fontaine

A convolution procedure is described for obtaining an analytical expression for the composition profiles of solute concentration:; in binary solid solutions. The free energy of solutions containing such compositional inhomogeneities can then be evaluated and the stability of spherically symmetric clusters (G.P. zones, for short) us a function of their radii and central compositions can be studied accordingly. Two characteristic zone radii are defined: the minimum radius (RM) corresponding to the smallest zone for which growth is energetically favored over dissolution, and the critical radius RK) corresponding to zones associated with the minimum work of formation. The values of RM and RK coincide at the two classical limits of nucleation and growth and spinodal decomposition. As the spinodal is approached, however, RM and RK diverge increasingly and it is proposed that the initial] decomposition morphology is governed more closely by the minimum, rather than by the critical radius since the former possesses no singularity within the m eta stable phase boundary. Reversion is briefly discussed in the light of the foregoing and it is shown that a set of reversion temperatures located between the coherent miscibility gap and the coherent spinodal must correspond to a given distribution of low temperature zones. SINCE the early works of Guinier1 and preston,2 the kinetics and morphology of GP zones have been studied extensively, see Ref. 3, for example, for a recent review. Nevertheless, a completely satisfying theoretical treatment of the decomposition of meta-stable or unstable binary solid solutions is still lacking due to the almost unsurmountable mathematical difficulties that one encounters in attempting to solve the pertinent diffusion equation which, in principle, describes the whole process. This equation, first derived by Cahn for the initial stages of spinodal decomposition,4 is a nonlinear partial differential equation of the fourth order in anisotropic space, a general analytical solution of which is completely out of the question. From this equation, some prediction can be made, however, concerning the later stages of spinodal decomposition5 and a recent numerical solution6 of the equation in the case of one- and two-dimensional composition modulations of a solid solution inside the spinodal has led to the following considerations: the sinusoidal morphology7 is to be expected only for solutions of average composition c, located near the center of the coherent miscibility gap.8 For solutions with co closer to the spinodal decomposition, depleted shell zones9 should constitute the first recognizable decomposition product, later evolving to iso- lated, enriched preprecipitates in a uniformly depleted matrix as this must, in all cases, constitute the final metastable morphology, barring, of course, loss of coherency and change in crystal structure. In agreement with the qualitative description of Bonfiglioli and Guinier,l0 it thus appears that the various models discussed by previous authors are, in fact, idealized successive stages of the general decomposition process. Unfortunately, corresponding calculations for a solid solution outside the spinodal are not yet available because of two additional difficulties: it is essential that the diffusion equation be solved in three-dimensional space, and furthermore, one must include in the equation an appropriate "source term" describing the statistics of the creation of composition fluctuations required to trigger the nucleation events. At present, a general treatment of this problem does not appear to be tractable. Nevertheless, by using a modelistic approach, i.e., by selecting a priori certain composition variation profiles and by evaluating their associated free energies, one can draw certain conclusions relative to the stability of these isolated composition modulations or "zones", both outside and inside the spinodal. This is the object of the present investigation. THEORY We shall now describe a standard four-parameter spherically symmetric GP zone, evaluate its free energy according to the Cahn and Hilliard11 formula (Eq. [5], below), and plot the corresponding energy surfaces as a function of zone amplitude and radius as

Jan 1, 1970

By A. Rosen, P. Wynblatt, J. E. Dorn

The temperature, strain rate, and structure dependence of the flow stress in a poly crystalline Fe-2 pct Mn alloy was investigated between 77" and 370°K. It was possible to identify the low-temperature data from 77° to 160°K with Dorn and Rajnak's theory of the Peierls mechanism of plastic deformation. Above 160°K one or more thermally activated mechanisms must he operative; however, these were not identified in this investigation. The mechanistic basis for the rapid decrease in the flow stress of bcc metals with an increase in temperature over the low-temperature range is yet being debated. Various dislocation mechanisms have been suggested in the past but the agreement between the various proposed theories and the experimental results have not been definitive. In the present paper, the authors will demonstrate that the plastic behavior of polycrystalline iron containing 2 wt pct Mn plus interstitials agrees excellently with predictions based on the Peierls mechanism from 77" to 160°K whereas from 160" to about 370°K other as yet unidentified thermally activated mechanisms take over. Undoubtedly, the overlap of these mechanisms with the Peierls mechanism contributed to the difficulties of rationalizing the low-temperature behavior of iron and its alloys. I) EXPERIMENTAL TECHNIQUES AND RESULTS Although extensive data are now available on the effect of temperature and strain rate on the flow stress of various bcc metals and alloys, it was, nevertheless, deemed necessary for the objectives of the present study to obtain highly accurate data of the type most pertinent for checking the theories on a series of well-documented work-hardened states. Iron containing 2 wt pct Mn was used in this investigation in order to obtain a lower ductile to brittle transition temperature than that for iron.' The additional elements present were 0.004 pct C, 0.05 pct 0, 0.004 pct S, 0.003 pct P, 0.006 pct N, and 0.001 pct Si. The as-received 3/8 by 3/4 in. bars were cold-rolled to 0.100-in. thickness, recrystallized under argon for 30 min at 1073"~, further cold-rolled to 0.063-in. thickness, and finally recrystallized under argon for 30 min at 1000°K. This treatment gave a stable reproducible equiaxed grain structure having an average grain diameter of about 90 p. Prior to the final recrystallization treatment, the sheet was machined into tensile specimens 1/4 in. wide having a 1.625-in.-long gage section. All specimens were tested in controlled-temperature baths on an Instron Testing Machine. For convenience in the theoretical analyses the data will be given in terms of the shear stress for flow, 7, the shear strain rate, f, and the shear strain, y. A series of three standard strain-hardened states were obtained by prestraining specimens at 300°K and at a shear strain rate of 7.68 x lo-' per sec to three stress levels of 6.89 X l08, 10.3 X lo8, and 14.5 x 10' dynes per sq cm, respectively. Immediately following this prestrain the temperature bath was changed and each specimen was pulled in tension at either f = 7.68 X lo-' or f = 3.06 X 10"3 per sec. In terms of the accuracy that was achieved, the values obtained did not deviate more than *0.1 X 10' dynes per sq cm and * 1°K from the reported values of stress and temperature and not more than *5 pct in the reported values of the strain rate. The tensile stresses were converted to shear stresses using a factor of 1/2. The shear stress for the initiation of flow at the test temperature was determined by taking a y = 6.16 x 10'3 offset. from the modulus line at which point good accuracy could be achieved in determining y and the associated flow stress 7, with only a negligible increase in the pre-

Jan 1, 1965

By H. M. Howe

It is a grave objection to the present system (or rather lack of system) of mineralogical nomenclature that, in the very great majority of cases, the name of a mineral gives no hint of its chemical composition, one might almost say no suggestion, however faint, of anything connected with it or characteristic of it, chemical, physical, historical, geographical, geological, or lithological. In becoming acquainted with a mineral, in addition to learning its composition and important characteristics, one must also learn a name wholly unconnected with any of them. It has occurred to me that a system might be devised in which the name of each mineral should express at least an approximation to its ultimate composition. It is far easier to learn the names of most minerals than their compositions. Most of us are familiar with the names and appearance of many minerals, especially among the silicates, of whose compositions we have but a rough notion. It would be the aim of such a system to enable us, in making the one slight effort of learning the name of a mineral, by that same effort and involuntarily to learn its composition, which now requires an additional and a much greater effort. I have worked out a system designed to meet this requirement, and its description occupies the remainder of this article. Doubtless there are many devices on which could be based other systems fulfilling the requirement above set forth better than that about to be described does, and at the same time furnishing names

Jan 1, 1884

By C. L. Sainsbury

Lode and placer tin deposits of the western Seward Peninsula, Alaska, have produced more than 2200 tons of metallic tin and constitute the only known domestic deposits of economic grade and size. The lode deposits consist of quartz-topaz greisens containing cassiterite and wolframite as well as numerous base-metal sulfide minerals, and most are in or near altered biotite-granite that forms isolated stocks or in rhyolitic dikes near granite. Within the main lode-producing area in the central York Mountains, nonpegmatite beryllium deposits, consisting principally of fluorite, chrysoberyl, diaspore, tourmaline, and white mica, with minor euclase, bertrandite, phenakite, hematite, and todorokite, are distributed zonally around the tin deposits and locally are transitional with them. All the known beryllium deposits are replacement lodes in carbonate rocks. In the area discussed, both tin and beryllium deposits are localized in a structural belt striking N70° to N85°E across the central York Mountains. The belt is characterized by numerous normal faults, which cut extensive thrust sheets, and by dikes of rhyolite, rhyolite porphyry, and lamprophyre that were injected along the faults. Ore deposits are localized where the dikes intrude brecciated rocks beneath thrusts and, although complex in detail, form tabular lodes that tend to lie along the thrusts. The granites contain abnormal amounts of tin, beryllium, lithium, and boron, and the tin and beryllium lodes are believed to be genetically associated with these enriched granites

Jan 1, 1968

By G. S. Coe, G. F. Bolling

The columnar-to-equiaxed transition (CET) has often been studied as a function of concentration, C, temperature gradient in the melt, G, and rate of solidification, R. Although it may not be immediately obvious it is sure that the CET, expressed as some ratio G/R necessary to suppress equiaxed nucleation for a given C,' cannot be a single-valued function of C. This restriction which is ignored in theoretical presentations is most trivially illustrated by the following simple reasoning. An ordinary casting is an unconstrained system where the thermal conditions change continuously with progressive solidification, and thus where the ratio G/R decreases from the outset. A CET occurring early in a casting (much equiaxed material) must then mean a higher value of G/R at transition, in comparison with the late CET which implies a more columnar ingot. Therefore, when we choose to experiment under constant superheat for all alloys across the simplest binary, and we find an inversion in the amount of equiaxed material, we shall find two values of C satisfying the G/R condition. However, in addition to this simple instance, the early experiments of ~orthcott' seem to show that the amount of equiaxed material in cast ingots may be a multivalued function of composition in a given binary system. In the present investigation, the CET has been examined in Pb-Sb, Pb-Ag, Pb-Sn, and Sn-Pb under several types of casting conditions. First, we have used the "bidirectional" ingot section Simulation;~ and we have used .'i~z situ" ingot solidification where a hot mold already filled with liquid is chilled so that there is no disturbance provoked by pouring. Differences in method are trivial to our purpose except for the fact that certain variations are more simply observed by one technique than by the other. Second, we have varied the mode of superheating from the simple extreme of casting all alloys from the same temperature regardless of composition to the careful casting at a standard superheat, calculated with respect to the alloy liquidus. Third, we have made provisions for decanting and interface observation, so that some "castings" were not completed. The results obtained with Pb-Sb are exemplary; some of these are shown in Fig. 1 along with explanatory captions. At 9 to 10 at. pct Sb, and thus above the solid-solubility limit Cs = 5.8 at. pct Sb and yet below the eutectic concentration Ceu = 17.5 at. pct Sb, there is a persistent anomaly in all the variations. Measurement was easy enough and standard enough so that we may forgo discussion of either method or possible error, in view of the forceful self-consistency shown by experiment. Solute distributions were measured along the bidirectional ingots in order to determine if a solute buildup had occurred at the CET. No anomalous changes in concentration were observed along the bars at either side of the solute anomaly of 10 at. pct Sb. The microstructures of the ingots were also examined across the range of composition investigated. At concentrations less than 9 at. pct Sb the micro- and macrostructures were typical of the cellular-dendritic growth usually reported for the columnar zone. Above the anomaly, both the columnar grain size and the amount of primary phase decreased. This microstruc-tural observation can be correlated with observations made of decanted interfaces. Below 9 at. pct Sb, the interface reveals the "normal" columnar dendritic structure; however above the anomalous concentration range, preferential growth of certain dendrites appears to form a "super dendrite" pattern. In Fig. 2 a microstructural view of the etched '(super dendrites'' shows their constitution both in terms of relative phase proportion and in terms of the ordinary smaller dendrites.

Jan 1, 1969

By J. P. Hammond, C. J. McHargue, S. E. Adair

Cold-rolled sheet textures have been determined for binary solid solutions of aluminum, columbium, tantalum, and zirconium in titanium. An alloy containing 3.8 pct Al had a (0002) [10101 texture, whereas alloys with the other elements had rotated (0002) [10101 textures similar to that of iodide titanium. THERE have been relatively few studies of the effect of alloying on deformation textures. A second element may be present in the base metal in solid solution and/or as a second phase. The literature offers no satisfactory explanation for the effects of solid solution alloying on textures noted thus far. For example, there is no satisfactory explanation of the difference in the textures of copper and a brass. The most complete study of the effects of solid solution alloying on deformation textures has been that of Brick, Martin, and Angier.¹ These investigators reported that the copper texture was retained by alloys of copper with up to 30 pct Ni, less than 5 pct Zn, less than 2 pct A1 or Co up to the limit of solubility. Copper containing more than 5 pct Zn, more than 2 pct Al, or the maximum soluble concentration of tin, silicon, or manganese showed the deformation texture of a brass. Bakarian² reported that additions of 0.20 pct Ca to 99.98 pct Mg or 2.0 pct Mn plus 0.15 pct Ca to magnesium resulted in entirely different textures than for the pure magnesium. The texture obtained for high-purity magnesium sheet showed the basal plane to be concentrated parallel to the rolling plane. The texture obtained for the alloy containing 0.20 pct Ca had the basal planes concentrated in elliptical areas whose centers were tilted 15" from the center of the pole figure toward the rolling direction. This split basal orientation was even more pronounced in the alloy containing 2.0 pct Mn and 0.15 pct Ca. Fuller and Edmunds" studied the rolled sheet textures in a zinc alloy containing 1 pct Cu and 0.01 pct Mn. The basal pole figure of this alloy contained a region of strong concentration not found in the pole figure for pure zinc.' In the above cases, results were discussed in terms of possible changes in slip and/or twinning systems and critical shear stresses. However, there were no experimental data to relate these speculations with the observed textures. It has been suggested that the deformation textures of titanium, zirconium, and beryllium could be directly ascribed to their low c/a ratios. The complex deformation mechanisms of titanium" also have been suggested to be characteristic of hexagonal close-packed metals with low c/a ratios. The purpose of this investigation was to study the cold-rolled sheet textures in binary titanium-base a alloys in which the c/a ratios were greater than, less than, and about the same as the c/a for iodide titanium. The annealed textures of these alloys will be reported in a subsequent article. Materials and Methods The chemical analyses of the metals used in this investigation are given in Table I. The alloys were prepared as 15 g buttons on a water-cooled copper block in a vacuum arc-furnace. The furnace was evacuated to pressures of the order of 10.' mm Hg, flushed with 99.98 pct pure argon, and melting was carried out in 0.2 atm pressure argon. Each button was remelted until radiographs and chemical analyses indicated complete solution of the solute elements. All buttons were forged and homogenized 72 hr at 500°C. The buttons to be rolled were ground and etched to sizes and shapes suitable for the rolling

Jan 1, 1954

By I. Zaplatynskyj, G. C. Kuczynski

SINCE the excellent studies of metal powder compaction executed by Kamm, Steinberg, and Wulff, no work on the subject has appeared in the technical literature. Kamm et al. were the first to investigate quantitatively the distribution of density in a powder compact, as a function of pressure, height and diameter of the die, powder particle size, etc. For this purpose they devised a very ingenious method. They inserted a thin lead grid into a die and then filled the die with powder. During cold pressing, the lead grid -moved downward. Due to its deformability it followed closely the downward descent of the adjacent powder. The die was then radiographed and, from the deformations of the grid openings measured on the radiographs, the density in the vicinity of each opening was evaluated. Their findings led them to the conclusion that the friction on the side walls of the die is a major controlling factor of the density distribution inside the cold pressed powder compacts. However, it is difficult to conduct tests similar to those of Kamm, Steinberg, and Wulff in a processing plant laboratory, which usually lacks the necessary expensive radiographic equipment. The purpose of this note is to describe a method which makes it possible to determine the density distribution in green powder compacts with the same accuracy as the lead-grid method but which is far simpler and faster and requires only standard laboratory equipment. Instead of using a lead grid, the hardness at selected points of the sectioned compact is determined. If the relationship between hardness and density is known the density distribution is readily obtained. This relationship is easily found from measuring hardness and densities of thin compacts. In such compacts the density, for all practical purposes, is constant throughout. The method was tested on a Plast nickel powder, grade FlA-A20, kindly supplied by Plast Metals Co. Thin compacts (height to diameter ratio 0.2) were pressed in a single action cylindrica1 die at various pressures. The density of the compacts was determined by weighing and by measuring the height and diameter with a micrometer. Subsequently the Rh hardness was determined. Up to ten readings were taken on each specimen. The difference in hardness readings on each compact was never greater than three corresponding to about 0.1 g per cu cm uncertainty in density. By varying the compaction pressure of the samples, a whole scale of densities was obtained allowing construction of a set of density-hardness calibration curves. To test the method several compacts of different height were pressed under varying pressures. Die walls were always well lubricated. After pressing, the compacts were mounted in bakelite and halved by grinding, and hardness readings taken along the diameters of the specimens. The distance between adjacent indentations was about 2.5 mm. After hardness readings were translated into densities, contour maps of densities of the compacts were prepared. One of them is reproduced in Fig. 1. The areas encompassed by the curves are labeled with numbers representing the density in g per cu cm of those regions. In Fig. 2 the same results are re-plotted to emphasize the radial density changes at various depths. The results thus obtained confirm the findings of Kamm, Steinberg, and Wulff kentioned previously. They are recapitulated here briefly. 1—The densest part of a compact pressed from one side is at the outer circumference at the top and the least dense part at the bottom, at the outer circumference. Figs. 1 and 2 show this clearly. 2—The density near the cylindrical surfaces of the compact decreases uniformly with height from top to bottom. 3—The density variation increases with the height to diameter ratio. References R. Kamm, M. A. Steinberg, and J. Wulff: Trans. AIME (1941) 171,'R. p. 439 ;MetaLs Technology (February 1941). R.p. Kamm, M. A. Steinberg, and J. Wulff: Trans. AlME (1949) 180, 2R.P. 694; MetalS Technology (December 1948).

Jan 1, 1957

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By Hubert O. DeBeck

The following descriptions and explanations apply specifically to the use of the Hotchkiss Superdip, but there are no apparent reasons why they should not apply to any magnetometer. This paper is a product of work in the practical field for several years with the Hotchkiss magnetometer, mostly on mineral deposits in the southeastern United States. The paper describes the result of an attempt to develop a practical and economical field method that approaches, as nearly as possible, the utmost accuracy of which the magnetometer is capable. As there are many published descriptions of various magnetometers and magnetic methods, it would be superfluous to describe such instruments here, but a limited bibliography on the Hotchkiss and Askania magnetometers is appended. The Hotchkiss and the vertical Askania magnetometers have, respectively, maximum sensitivities of approximately 5 and 30 gamma per instrument scale division. Purpose of New Method The purpose of the method described in the following paragraphs is to eliminate, as far as possible, all corrections of field data that cause complexities and inaccuracies in the results of magnetometer surveys. Magnetometer field observations must be corrected for periodic variations in the intensity of the earth's magnetic field, as well as for temperature variations, both of which take place during the course of a day. These variations do not seriously handicap magnetometer work on highly magnetic deposits, but it is impossible to obtain accurate results, by the conventional methods in use today, over weakly magnetic or diamagnetic deposits. This is due to the physical inability to obtain by such methods sufficiently accurate data in the field to make dependable corrections. The magnitude of the necessary corrections of field observations frequently exceeds the magnitude of local magnetic anomalies obtained over various types of mineral deposits. Therefore if these corrections are neglected or made on the basis of inaccurate data, the entire magnetic picture of the area concerned is at least distorted, and perhaps destroyed altogethcr.

Jan 1, 1934

By H. C. Meister

THE zinc-smelting industry of the United States has grown very rapidly in recent years and bids fair to outrival that of all other countries in the future. On account of the geographical situation of the chief ore-supplies, the industry may be divided into two main groups, the eastern and the western. The eastern and older group includes the works of Pennsylvania, New Jersey and Virginia, which practically control their own ore-supply. The western group includes the works of Illinois, Missouri, Kansas, Wisconsin and Indiana, which do not control their own ore-supply, but are compelled to buy the ore in the open market. It is for this reason that the western zinc-smelting industry has been undergoing continual changes since its inception 40 years ago. During the early discoveries of lead- and zinc-ore in the lead- and zinc-districts of Wisconsin and northern Illinois, the zinc-ore (sinithsonite or " bone " as the miner calls it) had no value and was considered waste; but later, when this ore was found in large quantities, it attracted the attention of metallurgists, which finally resulted, during the early sixties, in the building of the Matthiessen & Hegeler Zinc Works at LaSalle, Ill., the pioneer zinc-works of the West. A few years later, zinc-ore was discovered associated with the lead-ore in Jefferson county, southeastern Missouri, which started the industry at Carondelet or South St. Louis. Still later, the discoveries of zinc-ore in the lead-ore region, first' at Granby and then around Joplin, lead to the introduction of the industry in the southwest Missouri and Kansas districts. At first the development of the industry was slow, but it progressed steadily and it is now one of the leading metallurgical industries of the middle West.

Jan 1, 1905

In answer to inquiries from members, Mr. Sheafer said that the culm-banks of which his paper gave the shipments were of about the average quality of the banks in the Mahanoy region of the Schuylkill field,.made prior to 1881 or 1882, when the practice of preparing buckwheat coal was introduced; but that in a very old hank, made about 1849, no coal above pea-size had been found. Apparently it was then the practice to ship everything. In reply to an inquiry concerning the utilization of the fine coaldust, Mr. Sheafer said that it was not utilized in connection with the washing described in his paper, but was carried away in the water as waste; that during Mr. Corbin's presidency the Reading Company built at Mahanoy City an extensive plant for making artificial fuel, but difficulty was encountered, due to the circumstance that the small coal from different collieries varied in its combustible quality and also in the amount of pitch required to be mixed with it, and he believed they concluded that from some varieties of the coal-dust a very good fuel could be made, but at a cost entirely too great for successful competition with cheap coal. Of course, the anthracite dust was not so well suited to this manufacture as bituminous slack. R. W. Raymond, New York City : I believe that was the practical outcome of the enterprise of a member of the Institute, Mr. E. F. Loiseau, now deceased. It was found, I think, as an additional drawback, that the manufacture of artificial compressed fuel from anthracite dust could not be successfully practiced with material so impure as that of the culm-banks. Consequently, the manufacture could be based on that source of supply only when accompanied with a preparatory washing. The most favorable location for it would be at large yards where the waste from the handling of coal, which is comparatively pure material, could be thus treated. I believe the manufacture of compressed fuel from bituminous coal was at one time a profitable business in Nova Scotia, but was destroyed by the indirect effect of the general introduction of watergas for illuminating purposes. The result of that change on the

Jan 1, 1895

Discussion of the paper of CHARLES T. MALCOLMSON, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 271 to 289. E. W. PARKER, Washington, D. C.-The briquet or boulet, or coalette (whatever name is used) has come to stay as a part of the fuel supply, particularly for domestic purposes. During the past winter I have had some personal experience with the use of boulets made from anthracite coal. All of this winter I have used boulets in my furnacee and in my grate at my home in Washington. One reason for doing so is that we get the boulets at a price considerably cheaper than the prepared sizes of anthracite coal. The fuel has proved entirely satisfactory. One advantage possessed by the boulet is its absolutely uniform size, which makes the ventilation of the firebed practically perfect. The boulets burn until entirely consumed. There is not, even in an open grate fire, if the fire is kept constantly going, any unconsumed fuel passing through the grate bars. The boulets hold their form until entirely consumed and then break away into a clean white ash, with absolutely no clinker. That in itself is a particularly favorable recommendation to the housekeeper. Mr. Malcolmson has mentioned the fact that notwithstanding the smokeless character of anthracite, the boulets made from it emit smoke. The emission of smoke is due to the coal-tar pitch used as a binder. This is particularly noticeable if the fireman is somewhat careless, or wants to save labor, and feeds too much of the fuel on the fire at one time, cooling it down and thus causing an unnecessary amount of smoke. The smoke lasts but a short time, however, and if the fire is fed a little more frequently, with a small quantity of fuel at one time, the smoke is reduced to a minimum. I believe it will not be long before some of our engineers will have overcome the objectionable smoke; and will produce either from anthracite or from the so-called smokeless New River and Pocahontas semi-bituminous coals, a briquet which will be as smokeless as anthracite for all. practical purposes.

Jan 5, 1915

By H. M. Davis, J. H. Keeler

Densities of SAE 1020 (I) and ingot iron (II) decreased with cold rolling to minima at 60 pct reduction, whereas high-purity iron (III) was unaffected. I recovered promptly with annealing; II, sluggishly and incompletely. Hydrogen occlusion of III or II was barely affected by 60 pct cold reduction, but that of I was increased a hundredfold. IT has been reported of iron that its density is decreased and its occlusive capacity for hydrogen is increased by cold work. One of the most interesting aspects of each of these properties is that the changes brought about by cold work are not necessarily eliminated by annealing and recrystallization. Yet recrystallization is generally accepted as restoring to their original condition the properties or characteristics altered by cold work. A number of investigators have reported a decrease in density with cold reduction. Two1, 2 have shown that annealing after cold reduction may not return the density to its original value. It has been suggested' that cracks or flaws in inclusions produced during cold drawing contribute to the lowering of the bulk density of the metal. Extremely high-purity copper has been reported as not exhibiting a density decrease with cold reduction. On the other hand, calculations' indicated that grain distortion by itself can produce expansion of the order of magnitude of the changes observable. Maier" showed that both the density of iron and that of copper passed through a minimum with increasing cold reduction. Although much information is available on the subject of hydrogen in steel0, 7 and it is well known that plastic deformation of a metal may increase its occlusive capacity,8-12 most of the reports pertain to charging the metal with hydrogen by cathodic deposition or with acid. Darken and Smith,'" who employed acid charging, emphasized the great influence of cold work on the occlusive capacity of iron for hydrogen and showed the inability of a prolonged high-temperature annealing treatment to restore the occlusive capacity of cold-worked steel to the value exhibited in the hot-rolled condition. It has been reportedm that an "endothermic" metal*

Jan 1, 1954

By O. H. Hahn

I have lately had occasion to conduct a campaign at the works of the Empire City Company, in Railroad District, Elko County, Nevada, which, if not highly satisfactory, was at least very interesting in a technical point of view, and which I therefore think worthy of communication to the Institute. The lead ores in this district occur in lenticular masses along and near the contact of crystalline limestone with a dioritic porphyry, and consist of argentiferous carbonate of lead and galena, the latter occurring in solid blocks, or in ribbons running through the limestone. Associated with these are silicate, carbonate, and suboxide of copper, and brown and calc-spar. Adding to this, that the proportion of galena in the ore is small, and that no iron pyrites exists in the district, it is at once evident that the ore-mixture is difficult to treat. For a successful reduction by smelting, it would be necessary to introduce into the charge: 1. The proper quantities of sillphur-bearing ingredients, to effect a complete separation of copper and lead; and, 2. Sufficient silica and iron oxide, to form with the lime and magnesia of the ore, a slag of the required fluidity. The first condition could be fulfilled only very imperfectly, there being no iron pyrites in Railroad, nor in the surrounding districts. The nearest occurrence is in Battle Mountain, whence a supply could not be procured in time. The second condition, i. e., the addition of iron ore and quartz, was easily complied with, there being an abundance of these materials in the vicinity. The furnace of the Empire City Company, is a small shaftfurnace, with an area of hearth of six square feet, and is supplied with blast by a NO. 4 Root blower. In spite of this small size the furnace smelted during this campaign, which lasted 31 days, an average of 28 tons of ore, and 13 tons of fluxes, together 41 tons of charge, per twenty-four hours. The following tables give the complete data in regard to the smelting process, and the results obtained:

By A. J. Lanza

THE prevention of illness among the employees of the mining industry is especially important in view of the importance of the industry, the unsettled conditions of labor, which emphasize the economic necessity for conservation of labor, and for humanitarian reasons. The burden of chronic illness is altogether unwarranted and unnecessary. If the industry is to maintain its labor supply in an efficient manner and keep the standard high, it is essential that it make every effort to keep its labor in good physical condition. The basic principles underlying health conservation are the same for any industry, but they are here applied especially to the mining industry, and more particularly, perhaps, to metal mining, as it is with this phase of the industry that the writer is most familiar, and as it is conceded that metal mining presents more health hazards than coal mining. The first step in the prevention of illness lies in securing employees who are in sound health and free from organic disease. I do not mean that all men who go underground should be physically perfect, but they should be free from organic defects of the heart, lungs, and other organs, or from anatomical defects that would- markedly increase their liability to accident. The number of men working underground in mines in this country whose physical, condition totally unfits them for such work presents-a situation that should not be allowed to continue, and which I believe is 'not equalled in any other, industry in the country. There is but one way to secure men who come up to the required standard, . and that is by a thorough physical examination before employment. I am fully aware of the objections felt toward such a procedure by many employers and employees. There is much to he said on both sides, but to any one who is at all familiar with the mining industry as it is today in this country, and who approaches the matter with an unbiased mind, there can be absolutely no doubt as to the necessity for physical examination. As a purely logical proposition this is self-evident, but there remains the further necessity of placing physical examinations on such a

Jan 2, 1919