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By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The role of surface charge in soluble salt flotation, which was developed in Part I, is extended to relate the theory to the specific phenomena of KCI-NaC1 separations. Temperature-collector solubility relationships, metal ion activation, and particle size effects are discussed. The initial paper in this series developed and presented the hypothesis that one of the mechanisms of soluble salt flotation may involve electrical attraction between the collector and mineral surface. This hypothesis was developed from a combination of experimental data and free energy calculations, and details of the logic are presented in this first paper.* The studies have indicated that KC1 has a positive surface charge and NaCl a negative charge. KC1 can therefore be floated with sulfonate ion (RSO;) or with an aqueous polar species such as the aqueous amine chloride, RNH3C1(,,). The chloride end of the RNH3C1(,,) molecular dipole is probably negative and will be attracted to the positive surface of the KC1 particles and absorb (actually probably fit into a vacant chloride site) on the mineral surface. The amine end of the collector molecule would extend into the solution phase and provide the air avid surface required for flotation. NaCl particles are floated by such collectors as aqueous molecules of fatty acid salt, RCOONa(,,), in which the positive inorganic end of the dipole is attracted to the negatively charged surface of the NaCl and, in this case, adsorb and probably fit into a vacant sodium site on the surface. The aminium cation, RNH~, should also be a collector for NaC1. For certain collectors, actual precipitates of the collector must be formed before a sufficient amount of the polar aqueous molecule is present to effect flotation. In a system of this type there is a three-way equilibrium between: Aqeous Molecular Solid Precipitate - A of the Collector (Not Dissociated) . Ionic Species (Dissociated). The controlling equilibrium is probably between the precipitated form of the reagent and the aqueous

Jan 1, 1969

By James V. Luxner

The airflow and methane distribution patterns developed in an equipment-free entry 6.5 feet high and 12 feet wide, ventilated by line brattice operated blowing to or exhausting from the face, were determined by the Bureau of Mines for varying conditions. Results of these studies show that blowing line brattice systems of face ventilation are more effective than comparable exhaust systems. The face ventilating efficiency of any line brattice system is dependent upon the method of ventilation, the face distance, the tight rib distance, the volume of air delivered to the end of the line brattice, and the volume of methane released at the face. Experimental results indicate that maximum face ventilation efficiency is achieved when the inby terminus of the line brattice is installed 5 feet from the face and at a distance less than one-third the entry width from the nearest rib. Analyses of data are based upon the ability of a face ventilation system to dilute methane in the immediate face area.

Jan 1, 1969

By Forrest T. Moyer

The safety record of the metal mining and milling industries in 1965 is reviewed by the Bureau of Mines. The overall injury-frequency rate of 23.77 per million man-hours was 5 percent lower than in 1964 and was the lowest annual rate in a statistical history beginning with 1931. The injury-severity rate of 3,521 days lost per million man-hours in 1965 represented a 5-percent improvement over 1964. However, the total of 3,825 disabling work injuries comprised 61 fatal and 3,764 nonfatal injuries, one and 92 more, respectively, than in 1964. At primary nonferrous smelters, refineries, and reduction plants, the injury-frequency rate of 8.97 per million man-hours in 1965 was 13 percent lower, but the severity rate percent higher than in 1964. these plants in 1965, 4 more of 1,173 days lost per million man-hours was 17 There were 12 fatal and 971 nonfatal injuries at and 28 fewer, respectively, than in 1964.

Jan 1, 1969

By Verne E. Hooker

In situ stresses, based on isotropic and anisotropic relations, were evaluated using computer techniques from overcoring data obtained in dimension stone quarries along the Appalachian Piedmont, the Ozark Uplift, and the Ouachita Tectonic Belt. Stresses in the horizontal plane near the surface are compressive and range from 100 to 4,500 psi. The direction of maximum compressive stress seems to be alined with the general tectonic structure for most of the determinations. The ratio of the maximum to minimum elastic parameters in the horizontal plane ranges from 1.05 to 2.46 for these competent rocks. Isotropic versus anisotropic stress determinations show differences only as great as 25 percent in stress magnitude and 25° in orientation.

Jan 1, 1969

By Ross W. Smith, M. E. Wadsworth, T. James Smolik, A. S. Peck

Ross W. Smith (Acting Instructor, Department of Mineral Engineering, Stanford University, Stanford, Calif.) and T. James Smolik (Kennecott Copper Corp., Salt Lake City, Utah) - Professors Peck and Wads-worth have made an interesting contribution to the study of fluoride activation of beryl. We have a few comments to make regarding the paper and a question to ask of the authors. We note that glass containers were used in the study. Hydrofluoric acid should react with glass to produce SiFg2 in quantity which could adsorb onto the beryl surface (onto either beryllium or aluminum sites). The authors propose that individual F- ions actually go into the mineral surface lattice rather than onto the surface by adsorption of siFi2 ions. Based on infrared reverse bands with an untreated

Jan 1, 1969

By J. W. Downey, A. E. Dwight, M. H. Mueller, H. Knott, R. A. Conner

Sixty new ternary equiatomic compounds are reported with a hexagonal crystal structure that is isostructural with or very similar to Fe2P, D3h-P62m. HoNiAl is a typical example, with a, = 6.9893 ± 0.0003Å, C, = 3.8204 ± 0.003Å, and c/a = 0.54 7. Three holmium atoms occupy (g): x,0,1/2 three aluminum atoms occupy (f): x,0,0; one nickel atom occupies (b): 0,0,1/2; and two nickel atoms occupy (c): 4, + , 0. The nonequivalent 1(b) and 2(c) sites give rise to two sets of unequal interatornic distances (i.e., Ho-Ni and Al-NL in the case above), which account for the prevalence of Fe2P-type tertmry compounds and the scarcity of binary examples. Unit-cell constants are presented for the sixty compounds and density measurements on the compounds HoNiAl and UFeGa confirm that three formula weights are present per unit cell. Neutron and X-ray powder diffraction intensity measurements were made on CeNiAl and HoNiAl, respectively. The atomic posiLiotml parameters in CeNiAl were determined from neutron data to be x = 0.580 5 0.001 for cerium and 0.219 5 0.001 for aluminum. An investigation of the quasibinary section between the binary compounds CeNi2 and CeA12 revealed a new ternary compound CeNiAl. The compound has a hexagonal structure and is isostructural with the prototype compound Fe2P. Additional examples discovered or confirmed in this investigation provide a total of sixty ternary compounds that are isostructural with or closely related to Fe2P. Previous investigators1'2 reported the unit-cell constants for the hexagonal compounds UFeA1, UCoAl, UIrA1, ZrNiAl, ZrNiGa, HfNiAl, and HfNiGa and the present investigation has confirmed that the compounds are isostructural with Fe2P. Independently, Steeb and petzow3 reported the same structure type for UCoAl, UIrA1, and UNiA1. However, the present results suggest a different atomic site occupancy for the component atoms in the three compounds. A detailed investigation of the relative positions of the three kinds of atoms in the compounds CeNiAl and HoNiAl will be discussed. EXPERIMENTAL PROCEDURE The equiatomic alloys were prepared from elements of 99.9+ pct purity by arc melting under a helium-argon atmosphere. After homogenization at temperatures from 700" to 900' C, a metallographic examination was performed by conventional methods, and density measurements were carried out by the immersion method in CCl4. A powder sample was prepared for diffraction studies by crushing a portion of the annealed button. X-ray diffraction patterns were obtained with a Debye-Scherrer camera, in which the annealed powder was glued to a quartz filament, and indexed with the aid of a Bunn chart. Unit-cell constants were calculated from the computer program of Mueller, Heaton, and Miller4 and d spacings were obtained by the program of Mueller, Meyer, and Simonsen.5 The intensity values were calculated from the relation I, ~ (m)(L.P.)F2 by a computer program written by Busing, Martin, and Levy.6 The absorption and temperature correction factors were neglected. An X-ray study of HoNiAl was carried out to take advantage of: large differences in atomic scattering factors for holmium and aluminum, X-ray patters free of background darkening, negligible oxidation at room temperature, and negligible weight loss in the preparation of this alloy. The neutron diffraction studies were made on a powder sample of CeNiAl contained in a -in. diam V tube and a pattern was obtained with neutrons of wavelength The neutron scattering factors employed (x 10-12 cm). In contrast to the scattering amplitude for X-rays, cesium does not have the largest cross section, however, there is a sufficient difference in the neutron scattering amplitudes to distinguish between the atomic species. The neutron transmission was high, 86 pct; therefore, absorption corrections were not necessary for the cylindrical sample. Most reflections could not be observed individually, because of the relatively large unit cell (a = 6.9756 and c = 4.0206Å) and relatively short neutron wavelength; therefore, the intensity of grouped reflections was considered. The Kennicott modification7 of the Busing-Martin-Levy program6 was employed to determine the identity of the atoms at the various lattice sites and the positional parameters. RESULTS A structure for the prototype compound Fe2P was first reported by Hendricks and Kosting;8 however, the structure was in error. The correct structure, as reported by Rundqvist and Jellinek,9 is as follows. The unit-cell constants and volumes per formula weight (V/M) are given in Table I for the sixty compounds examined in this investigation and classified as Fe2P-type compounds. The structure type was determined initially from a comparison of the unit-cell constants of HoNiAl with other known examples of this structure type1' and from the density of HoNiAl, given in Table 11. The density indicated that three formula weights comprised a unit cell, as in the prototype compound Fe2P. The assignment of the three species to lattice sites was made initially on the basis of atomic size. The large holmium atoms were assigned to the 3(g) sites that have a relatively large interatomic distance to nearest neighbor positions, the small nickel

Jan 1, 1969

By David D. Rabb

Leaching or solution mining, a relatively simple and economical process for beneficiating metallic ores, is likely to find increasing application in the treatment of low-grade ores that are impractical to mine by any other means. This process may be carried out in two different ways: 1. Dump leaching, where the ore is moved from its original location to be leached at another site. 2. In situ leaching, where the ore is leached in place by introducing the leach solution at the top, letting it flow down through the ore under gravity, and then recovering it plus the dissolved metals it contains.

Jan 1, 1969

By William O. Rasmussen

Exploration requires processing highly varying kinds and amounts of geologic information. Successful discovery dictates that this be done quickly with maximum confidence. Most phases of exploration are more or less applicable to computer reduction on a routine basis. The use of digital computers to reduce raw data into interpretable form, lets the exploration geophysicist concentrate on interpretation and presentation, and to consistently apply more sophisticated and comprehensive analytical techniques, not practical before. In applying these concepts for the past several years, various efficient programs have evolved which provide more complete evaluation of all data including the pro- vision for more unique solutions. This has resulted in greater refinement and ability to select the most advantageous drill sites in a minimum time at a minimum cost or, in rejecting as soon as possible a project on which additional effort is no longer justified. Practical examples of computer applications in magnetics (air and ground), induced polarization and resistivity are discussed.

Jan 1, 1969

By L. C. Brown, A. J. Stewart

Phase transformations have been studied in Ag-Zn alloys quenched from the high-temperature bcc 0 phase and lying in the composition range 37.4 to 50.0 at. pct Zn. On quenching, the alloy with the lowest zinc content transformed to massive a (fcc); all other alloys formed the ordered (3' phase. On deformation, a martensitic reaction took place forming a close-packed structure. At Lou' zinc contents transformation to this structure was complete. However, above 43 at. pct Zn a p.rogressively increasing amount of ß' was retained following deformation. The close-packed structure was fcc at lower zinc contents (under 47 at. pct Zn) and either hcp or a mixture of fcc and hcp at high zinc concentrations. The structures produced by cold working were unstable and on aging transformed to the ß' phase or the complex hexagonal to phase. For low zinc contents (under 43 at. pct) the fcc st-ructure transformed directly to the equilibrium To phase. With higher zinc contents, some 13' was retained following defownation, and on aging the amount of this phase relative to the close-packed structure increased. On further aging both structures transformed cornpletely to PO. Metallographic examination indicated that the nature of the deformation product depended very markedly on the mode of deformation. Tensile deformation gave a microstructure characteristic of thermal martensite. KING and Massalski1 have shown that an alloy of Ag-50 at. pct Zn quenched from the high-temperature bcc ß phase undergoes a low-temperature ordering reaction forming ß' which can be retained to room temperature. On deformation an hcp phase is produced, although this is unstable and the structure reverts completely to ß' on aging. In the present paper, the work of King and Massalski is extended to cover a wide composition range in the p phase, observations being made of the structure of the quenched 13 and of the effects of deformation and aging. The relevant portion of the Ag-Zn phase diagram is shown in Fig. 1. King and Massalski have shown that close to stoichiometry the ß' phase is the equilibrium structure at low temperatures. The approximate composition range of this phase, taken from a recent paper by Pops and Massalski,3 is shown on the phase diagram. The locations of atom sites are very similar in the ß' and to structures, and the 4, structure can be derived from the 0' structure by a small movement of atoms mainly in the direction of the cube diagonal.4'5 However, the probability of filling any particular atom site by a silver or a zinc atom is markedly different in the two structures. The structure can be considered partly ordered but the arrangement of the ordered atoms is completely different from that in the p' structure and transformation from ß' to requires a large fraction of the atoms to change position. It has been shown that the ß' transformation is thermally activated involving normal nucleation and growth processes.5,8 Massalski and Barrett7 have shown that in the Cu-Zn binary the (3 phase can be retained in the ordered state to room temperature over a wide composition range. On deformation a new close-packed phase is produced, the structure varying from fcc to a mixture of fcc + hcp to hcp alone with increasing zinc concentration. It appears that an ordering reaction is necessary to retain the bcc phase to room temperature. In CU-Ga,8 the bcc phase cannot be retained to low temperatures as it transforms by a massive reaction above the ordering temperature of the ß phase. The structure of the massive phase is very similar to that in Cu-Zn, varying from fcc to fcc + hcp to hcp with increasing zinc concentration. Similar structures have also been observed in CU-A1,9 Ag-Cd,10,11 and Ag-Al.12 EXPERIMENTAL The alloys were prepared by melting fine silver (99.99 pct purity) and electrolytic zinc (99.999 pct

Jan 1, 1969

By P. T. Chiang

Chemical etching methods for the simultaneous revealing of the tellurium or selenium Phase and the chalcogenide grain boundaries of the alloy systems are given. A tellurium eutectic was found Present in zone-melted ingots. Similarly, a selenium monotectic was present in ingots. In general, the second phase (tellurium or seleniumn) occubies three different sites; viz., along the chalcogenide grain boundaries, as inclusions within the chalcogenide grain, and on the undersurface of the ingot. The detection limit for the tellurium phase is about 1 u in width. THERMOELECTRIC materials based on Group V (bismuth, antimony) and Group VI (selenium, tellurium) elements have aroused considerable interest in recent years in the practical application of thermoelectric cooling. In many cases, a small amount of excess tellurium (or selenium) was added to the material to optimize its thermoelectric properties. Then the question immediately arises as to the number of phases present in the resultant alloy. In the binary systems of Bi-Te, Sb-Te, and Bi-Se, the congruent melting compositions have been reported to be non-stoichiometric and are represented by Bi~Te respectively. It is to beexpected and known that Bi2Te3 and SbzTe3 crystallize from the melt with an excess of bismuth and antimony in the lattice and that tellurium forms a eutectic.~' The same could be assumed to take place in the pseudo binary systems of (Bi,Sb)zTe3 and Bi2(Se,Te)3 as well as in the system studiedby puotinen5 and other workers. Likewise, BiaSe3 crystallizes from the melt with an excess of bismuth in the lattice and selenium forms a monotectic.~ Therefore, in practice, alloys solidified from the melt often contain a second phase (tellurium or selenium) in one region or another of the solid mass even without the addition of excess tellurium (or selenium). ~u~~recht' studied the thermoelectric properties of (Bi,Sb)2Te3 alloys with excess tellurium and simultaneous additions of selenium. He mentioned that the materials show two phases because of the considerable excess of tellurium or selenium. However, he did not report as to how the tellurium or selenium phase was identified. It is generally believed that the presence of an excessive amount of tellurium or selenium phase in the alloy would adversely affect its thermoelectric properties and its uniformity. Consequently, there is a need for a simple method for the identification of the tellurium and selenium phase. The quantity of the second phase present is usually too small to be detected either by chemical analysis or by normal X-ray techniques. This investigation was therefore carried out, first, to devise a simple metallographic method for the identification of the tellurium or selenium phase coexisting with the chalcogenides and, second, to determine the distribution and specific location of the tellurium or selenium phase in the ingots. EXPERIMENTAL PROCEDURE The starting materials used for the alloy preparations were 99.999 pct pure bismuth, antimony, and tellurium and 99.997 pct pure selenium. The bismuth and antimony were obtained from Consolidated Mining and Smelting Co. of Canada Ltd., while the selenium and tellurium were obtained from Canadian Copper Refiners Ltd. The tellurium was purified further in the laboratory by zone refining. The elements were pulverized in a stainless-steel pestle and mortar. The amounts for the desired composition were weighed out each time on an analytical balance to make up a 100-g sample. Then the sample was introduced into a Vycor ampule (19 by 150 mm), pumped down to a vacuum of 10"5 Torr for 15 min, and sealed off. The ampule was then heated in a horizontal resistance furnace at 800" to 900°C for about 20 hr. During this period the assembly was rocked back and forth several times to ensure good mixing. At the end of the heating period, the ampule was quenched in cold water and then transferred to the zone-melting apparatus described in a previous publications to grow large-size aligned polycrystals. The background and ring-heater temperatures were adjusted to make the freezing solid-liquid interface slightly convex to the liquid. The recorded temperature gradient in the vicinity of the freezing solid-liquid interface was around 15°C per cm. The ampule was moved horizontally at a speed varying from 0.4 to 2 cm per hr so that the ring heater would cover the whole ingot length from end to end. A single zone-melting pass was used for the Bi-Te, Sb-Te, and Bi-Sb-Te ingots. Two passes in the forward and reverse directions were carried out for the Bi-Se and Bi-Se-Te ingots. Six passes in the forward and reverse directions were performed for the Bi-Sb-Se-Te ingot. The zone-melted ingots were found to contain several large crystals, with their basal planes (0001) approximately parallel to the growth axis. Samples of bismuth and antimony tellurides coated with a layer of tellurium, and bismuth selenide coated with a layer of selenium, were prepared for comparison in phase identification. These coatings were made by dropping a piece of the zone-melted ingot into some molten tellurium or selenium under argon atmosphere and allowing them to cool slowly to room temperature. The metallographic specimens were prepared by

Jan 1, 1969

By David A. Sterling

Approximately 50 percent of the uranium resource of the Free World is in deposits of Precambrian age, principally in lower Proterozoic conglomerates in Canada and South Africa (Uranium Resources, Joint Report, ENEA and IAEA, 1967). Most of the uranium resource of the United States is in Mesozoic and Cenozoic continental clastic sedimentary rocks that fill intracratonic basins. The Atomic Energy Commission is investigating the distribution of uranium and thorium in the Precambrian of the Western United States and the relationship of, time-space-facies patterns of uranium and thorium enrichment in the Precambrian to the major resources of uranium in the Mesozoic and Cenozoic host sedimentary rocks. This paper summarizes the results of preliminary studies of the Precambrian in the Southwestern United States including New Mexico, Arizona, southern Nevada, and southern California (Fig. 1). The host rock provenances for the major uranium resources in epigenetic deposits of Mesozoic and Cenozoic age in the Western United States were in areas of extensive Precambrian exposure along the eastern margin of the Phanerozoic geosynclinal belt (Fig. 2). Mesozoic continental clastic sediments in the Colorado Plateau contain about two-thirds of the uranium resource of the United States. These sediments formed from detritus derived from the Mogollon highland in the Southwestern United States where the Precambrian was extensively exposed (Stewart, et al., 19593 McKee, et al., 1959; McKee, et al., 1956; Craig, et al., 1955) (Fig. 2). A genetic relationship may exist between this provenance and the major uranium deposits of the Colorado Plateau. The Precambrian might be equally important in the genesis of uranium deposits whether the most important process in the formation of these deposits was the leaching of low-order intrinsic amounts of uranium from Precambrian granite or from Mesozoic pyroclastics derived from syntexis of the Precambrian basement rocks (Malan, 1968).

Jan 1, 1969

By D. H. Forbes, H. M. Manasevit, F. L. Morritz

Single-crystal thin films of molybdenum have been grown. by the pyrolytic decomposition of molybdenum hexafluoride in a hydrogen ambient on various insulating substrates at temperatures front 650° to 900° C. Single-crystal discs of various orientations of magnesium aluminate spinel, a aluminum oxide, magnesium oxide, and the natural facets of beryllium oxide were all observed to exert epitaxial control on the depositing film. Determinations of the crystallographic relationships existing between film and substrates have been made, using X-ray diffraction three-circle goniometry and Laue back-reflection techniques. Using these data, crystallographic overlays have been constructed which suggest a possible interfacial geometry on the basis of a match between metal deposit atoms and metal ion sites in the substrate. A continuing program has been in effect in the Auto-netics Laboratories over the past several years aimed at the development of electronic materials in new and useful forms using chemical vapor deposition techniques. During the course of these investigations, the epitaxy of silicon1"5 and tungstenep7 on single-crystal metal oxide insulators was studied extensively. The deposition of molybdenum is a logical extension of the tungsten work since the crystal structure is identical and the lattice dimensions differ by less than 1 pct. The pyrolytic decomposition of molybdenum hexafluoride in hydrogen was used to grow molybdenum films on the oxide substrates AlzOs, MgA1~04, MgO, and Be0 at from 650" to 900°C, depending on the substrate material. Under the experimental conditions to be described, monocrystalline films of controlled orientation were obtained. The materials investigated and their crystal structure are listed in Table I. EXPERIMENTAL The molybdenum depositions were effected by the hydrogen reduction of molybdenum hexafluoride (MoFe) in a flowing system of hydrogen at atmospheric pressure. The schematic of the apparatus is shown in Fig. 1. The hydrogen, purified by passage through a heated palladium thimble, was mixed with the vapor of the liquid MoFe maintained in a steel bottle at room temperature (25°C). The mixture was passed over the substrate, which was heated by rf induction of a sup-

Jan 1, 1969

By J. A. Goebel, S. Rosen

IN the NiAl phase diagram the NiAl (CsC1-type) phase field extends over a large composition range. At elevated temperatures the nickel-rich phase boundary extends to a composition of about 70 at. pct Ni, a value which is within 5 at. pct of the Ni3A1 (Cu 3 Au-type) phase boundary.' At room temperature, however, the maximum nickel content is only about 60 at. pct. Experiments have shown that alloys containing greater than 63 at. pct Ni when quenched from temperatures below 1000°C contain the equilibrium phases NiAl and Ni3A1. On the other hand, when these same alloys are quenched from temperatures above 1000°C and examined microscopically, a typically martensitic decomposition product appears in the microstructure as shown in the micrograph of Fig. 1. The structure of the martensitic phase has been determined by employing powder X-ray diffraction techniques to be an "ordered" AuCu type (Strukturbericht Llo, space group P/4 mmm - DL). The diffraction pattern of this phase differs from that of AuCu in the appearance of superlattice lines. The structure is shown in Fig. 2. The open circles represent nickel atoms and the half-shaded circles represent nickel and aluminum atoms which are randomly distributed. The sites represented by half-shaded circles would be occupied solely by nickel atoms at a stoichiometry of Ni3A1. The alloys used in this investigation were prepared from 99.99 wt pct Al and 99.99 wt pct Ni by arc melting charges of varying compositions in a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. In all cases chemical analysis agreed within $ at. pct with the nominal compositions of the alloys. Annealing treatments were carried out in a vertical resistance furnace through which a stream of argon gas was flowing. Specimens, which were wrapped in tantalum foil, were quenched by allowing the specimens to drop into a bucket containing iced brine. X-ray diffraction patterns were obtained from -325 mesh powder specimens by using a 114.8-mm

Jan 1, 1969

By E. Zucker

In this paper, as in the 1960 CIM paper of the same name, s1gmf1cant new developments in electrical-mechanical mining equipment are briefly described. These include static thyristor-supplied D.C. drives for mine hoists, load-haul-dump systems, process controls with small and medium-size computers, and several other new items of equipment and Concepts. All the new hardware descriptions are given in the context of over-all process integration. This means the actual mechanical linking together of two or more processes and the preliminary step in the development of production-line mining.

Jan 1, 1969

By H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher' estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,' however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,' in his test of Cottrell's theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell's theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley's assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12'13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a', an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

By Robert L. de Beauchamp

The Bureau of Mines reviewed aluminum chloride technology to determine the problems associated with its preparation from minerals, and to ascertain the best areas for research to solve these problems. Commercial AlC13 production processes are described and the ?state of the art? for the preparation of AlC13 from aluminous materials is evaluated. Areas for further research are indicated.

Jan 1, 1969

By Clarence O. Babcock

Model pillars of limestone, marble, sandstone, and granite with length-to-diameter (L/D) ratios of 3, 2, 1, 0.5, and 0.25 (0.286 for granite) were tested to failure in axial compression to determine to what extent an increase in end constraint increased compressive strength. Adjustable steel rings, mechanically tightened about the ends of test specimens to create a radial prestress of 3,000 or 5,000 psi prior to the application of axial load, increased end constraint more than was possible in previous tests using solid steel rings. (Solid rings, epoxy-bonded to the ends of dogbone specimens, increased compressive strength compared with that of straight specimens without ring constraint.) During the loading cycle, additional end constraint was produced by lateral expansion of the specimens against the rings. The effect of the end constraint was to increase the compressive strength 55 to 58 percent for the shorter pillars of dogbone shape compared with the compressive strength of straight pillars with the same L/D ratios without ring constraint. Most pillars with L/D ratios of less than 2 were made stronger by end constraint. Pillars with an L/D ratio of 3 did not benefit significantly from end constraint. When the results from compression testing of straight specimens of rock in the laboratory are used to design mine pillars in situ, the pillars will be larger than necessary if the horizontal compressive stress is several thousand pounds per square inch greater than that resulting from the weight of the overlying rock alone. The L/D ratio can be increased by a factor of 1.76 for ratios in the range 0.25 to 3 and still provide the same compressive strength. The safety factor applied with straight specimen test results should also be acceptable for use with constrained pillar test results.

Jan 1, 1969

By R. E. Siemens

The Bureau of Mines sought to correlate the variation of structure-sensitive superconducting properties with microstructure in selected Cb-Hf alloys and to compare the experimental results with those predicted by the GLAG theory. Alloys in wire and rod form were evaluated by critical temperature, critical current, magnetization, resistivity measurements, and optical and electron microscopy. In the absence of an external magnetic field, the current carrying capacity of columbium was greatly reduced with addition of up to 85 wt pct Hf, but a large increase in Ic occurred for Cb-90 wt pct Hf. Favorable Ic-H behavior was observed in cold-drawn alloys containing 25 and 57 wt pct Hf. Correspondingly, a maximum in Tc occurred at 10-25 and 90 wt pct Hf. Four- or five-hour heat treatment at 600° C resulted in maximum Ic values and maximum hysteresis in magnetization. Dislocation pileup, polygonization, and fine precipitates, responsible for flux pinning, are listed in order of their effectiveness as pinning sites. Sites having an average separation of 1,500 to 3,000 A and a diameter of 1,000 A or less were most effective in influencing Ic-H and M-H behavior. The resistive critical fields increased smoothly to a maximum of 80 k0e between 60 and 65 wt pct Hf. Highfield, mixed state, reversible paramagnetism was observed in some alloys; however, the GLAG theory was in good agreement with experimental results for the majority of the composition range studied.

Jan 1, 1969

By Edwin B. Wilson

Electric power generation remains the greatest market for coal in the United States. In 1967, about 272 million tons of coal, amounting to over 51 percent of total coal consumption, were burned to satisfy this nation's hugh demand for power. The size of the utility market is currently five times that of 1941 and continues to grow with the demand for more and more energy. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F.

Jan 1, 1969

By G. H. Keith

The Bureau of Mines determined the mechanism(s) involved in observed anomalous changes in mechanical properties of vanadium-base alloys. Tensile properties of electrorefined and commercial-purity vanadium-base alloys containing up to 5 atomic percent molybdenum or titanium were measured between 77° and 673° K. Snoek oxygen and nitrogen peak heights were measured to determine the changes in dissolved interstitial content caused by increasing quantities of solute. In addition, changes in lattice parameter were followed wit: precision X-ray techniques. Softening, observed in alloys containing titanium, is explained by the formation of a second-phase titanium compound with oxygen or nitrogen. However, because of partitioning of titanium between compound formation and solid solution formation, about five times the stoichiometric amount was required for complete reaction. Addition of 1 percent titanium drastically lowered the strengthening due to strain aging, at 673° K, and 2 percent titanium essentially eliminated it. All alloys were ductile at 77° K. Variations in the tensile properties of the molybdenum-containing alloys are explained by variations in the amounts of interstitial impurities present. The molybdenum did not react with these impurities and had no effect on strengthening due to strain aging. Commercial-purity vanadium alloys containing more than 2 percent molybdenum were brittle at 77° K.

Jan 1, 1969