Search Documents

By N. J. Grant, D. S. Bloom

N recent reports, Sully' and Beck and coworkers' I have advanced hypotheses concerning the formation of the phase. Both of these hypotheses are based on Pauling's theories of the electronic configuration of the elements of the first transition group. Sully considered that the number of electrons which can be absorbed in filling electron "holes" is the factor which determines whether or not the structure can form. Beck suggested that the presence of a certain concentration of electron "holes" is the controlling value. It can be shown that a similar criterion can be developed without making reference to Pauling's theories. Table I shows the elements of the first transition group and the incidence of the a structure in the binary systems of these elements according to the data presently available. Also appended is the number of electrons considered to exist in the 3d-4s levels of these elements. If the atomic percentages for the phase are listed as shown in Table 11, and if the number of electrons in the 3d-4s levels per atom is calculated for the a boundary values, the results are as shown in the last column. It can be seen that the numerical values are all in the vicinity of 7 electrons per atom. This is true also for the ternary Cr-Mo-Ni IT phase, which occurs in a system in which none of the binary compositions are known to develop the phase. In the Fe-Mo binary, the high temperature a phase, which occurs at a composition of 50 atomic pct of each element, also yields a ,;1 e of 7 electrons per atom. From inspection of Tables I and 11, it develops that any series of sequential numbers which is assigned to the elements under consideration will result in the numbers pertaining to a compositions grouping themselves around one specific number. It does not follow, however, that this random number necessarily has physical significance. Such a point has already been discussed by Hume-Rothery." One interesting point develops from this study, however, and that is the position of manganese with reference to the other elements and to the phase. In the system used here, the formation of phase is associated approximately with the value of 7 electrons per atom, which is also the number of electrons per atom that manganese has. Manganese, it will be recalled, exists in three different crystal forms, none of which are the usual, simpler metallic forms; on the other hand, elements just to the left of manganese (in Table I) generally have lower coordination-number structures (body-centered cubic) than do elements to the right of manganese (face-centered cubic). The contribution to a complex crystal structure by the interalloying of elements from opposite sides of manganese is significant in that the a phase is formed in binary systems including one element from each side of manganese, with manganese capable of participating with both sides. It is indeed an interesting coincidence that manganese, with 7 electrons per atom, solidifies in complex crystal forms, and that when alloys of the transition elements are made which have seven 3d-4s electrons per atom, they, too, tend to assume a complex crystal form. From the above, it might be deduced that the study of the a phase might be advanced by a critical examination of the element manganese and how its structure is affected by small additions of elements which change the 3d-4s electrons per atom number. The role of atom size would also be of interest in formation. References ' A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, Part 4, p. 173. 2 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951). "W. Hume-Rothery, H. M. Irving, and R. J. P. Williams: The Valencies of the Transition Elements in the Metallic State. Proc. Royal Soc. (September 1951) 208A. p. 431.

Jan 1, 1954

By Ferid Kromer

Geography: The Tagtepe district of the Vilayet of Eskigehir is about 20 miles northeast of the city of Eskigehir (approximately midway between Ankara and Istanbul) in western Anatolia. The area is a mountainous one, the highest peak being Tagtepe Mountain (5200 ft) which is approximately in the center of the district. The mountains drop off to the deep valley of the Sakarya River on the north and to the plain of Eskigehir on the south. FERID KROMER, Junior Member AZME, is a Consulting Mining Engineer and General Manager, Bagtag Turk Maadin Ltd., Istanbul, Turkey. New York Meeting, February 1950. TP 2629 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Dec. 29, 1948. For the most part, the watershed is on the northern side of the mountain barrier, draining into the Sakarya River, which in turn empties into the Black Sea midway between Zonguldak and the mouth of the Bosphorus. The approximate area covered by the Tagtepe district is shown in fig. 1. Transportation to shipping points is available via the Istanbul-Ankara railroad. The station on this line nearest the mining district is Alpikoy station, about 20 miles by road southwest of Tagtepe Mountain. Interior roads within the district are poor. Being of dirt, the winter rains and snows render them almost impassable for trucks from about the middle of December until the end of March, thus presenting a considerable transportation problem. However, the roads from the Bagoren and Tagtepe chromite mines to the railroad shipping point at Alpikoy station have recently been repaired and will be maintained for all-weather truck transportation. Detailed climatic data are not available. However, in general the spring, summer, and early autumn months are dry, and good weather may be expected from May until early November. Then the winter rains commence, and heavy snow is usual during January and February. Geology: The mountainous structure of Tagtepe belongs to basic rocks of serpentine (Variscan Orogeny) which is in contact with Paleozoic schists at west, and an Oligocene outcrop of red clays in Margi-Sepetci region (see fig. 1) at southeast. The northwest and southwest borders of Tagtepe district are, respectively, surrounded by Paleozoic schists and pebbly gray and yellow Neogene clays. More recent formations of alluviums overlay the plain of Eskigehir. Dark basic rocks of trachytes with hornblende are visible on Turkmenbaba Mountain, at the west of Tagtepe. Mineral Occurrences: Chromite: the most important mineral found in any quantity in the Tagtepe district. The alignment of the deposits of chromite is in general along the line Bagoren-Tagtepe (see fig. 1). The first mines in the area were those of Tagtepe and Bagoren, which were developed over 20 years ago with Swedish capital. Other deposits of chromite, more recently discovered and so far of less importance, are being worked at Kurucor, Komurcu, Gelinmezari, and Lacin (see fig. 1). Deposits average generally between 46 and 48 pct chromic oxide, with the exception of the Bagoren mine which averages 44 pct. However, a new lode, very recently plotted, in the Tagtepe mine averages 50 pct Cr,O,, 4.6 pct SOz, and 7 pct FeO. Geological character of the chromite occurrences in the Tagtepe mine may be considered typical of most chromite lodes in this area. The indications are that the formations of ore lenses are developed by the segregation of chromite crystals intruded into the serpentinized rock, and exposed later to tectonic movement within the zone of crystallization. All lenticular masses are more or less regular in shape and follow each other in southeast-northwest direction and dip generally 70" NE. Ore lenses do not seem to persist in depth, average depth of two lenses is 60 ft below surface. Three lodes .have been mined as open-pit. The average dimensions of individual lenses are as follows: pitch length, 100 ft; breadth, 27 ft; and width, 20 ft. The lenses and their enclosing rocks are broken by parallel fractures in approximately east-west direction. These joints are filled, except in one lode, with cementing material, which gives to the ore a

Jan 1, 1951

By G. Osuch, G. Derge, G. M. Pound

Using a new dternating-current potentiometer circuit and a specially designed four-terminal cell, the specific conductance of molten Cu2S-FeS mattes was measured as a function of temperature, from the liquidus to 1500°C, over the complete range of composition. The high conductivities, about 1500 ohm-I cm-l for FeS and 100 ohm-l cm-l for Cu,S, indicate that the conduction is electronic rather than ionic. Molten FeS has a negative temperature coefficient of specific conductance, resembling metallic conduction. Molten Cu,S has a positive temperature coefficient, resembling semiconduction. The binary roughly follows an additive rule of mixtures with respect to both magnitude and temperature coefficient of specific conductance. Metallic bonding in the liquid is postulated to explain these phenomena. MUCH has been learned in the past about the nature of liquids and the ionic or molecular species in solution by means of electrical measurements. Thus, dielectric constants','2 have given information about molecular liquids such as water and benzene. Measurements of dielectric constant usually are impossible in electrically conducting liquids, such as aqueous solutions of ionic salts and molten ionic salts. However, measurements of electrical conductance and ionic transference have provided much knowledge about the latter systems.a-" In recent years, the ionic nature of certain molten metallurgical slags has been established by Derge and Martin7 through electrical conductance and electrolysis measurements. Chipman, Inouye, and Tom-linsonq ave studied the electrical conductance of molten FeO and report a high specific conductance of about 200 ohm-' cm-' (compared with 4 ohm" cm-' for an ordinary ionic liquid such as molten NaCl) and a positive temperature coefficient of conductance. They interpret these results in terms of p-type semiconduction by analogy to the situation in solid FeO.Y imnad and Derge" have studied cell efficiency in the electrolysis of molten FeO-SiO, systems and conclude that ordinary ionic conductance increases with SiO, content. Very recently, interest has been revived in the electrical conductance of liquid metals and liquid metallic solutions. Scala and Robertson1' report a close resemblance between the liquid and solid states with respect to thermal, structural, and compositional relationships. Molten sulphides have not received a great deal of attention. Bornemann and von Rauschenplat" measured the specific conductance of molten Cu2S as a function of temperature with a four-terminal cell using direct current. A high specific conductance and a positive temperature coefficient were found in that investigation." Using a two-electrode apparatus, Savelsberg" electrolyzed various molten sulphide mixtures. He concluded that pure molten Cu,S and FeS were electronic conductors but that the mixtures exhibited some ionic conduction. In the present investigation, the specific conductance of the industrially important Cu-Fe sulphide mattes was measured as a function of temperature and composition in order to investigate the mode of electrical conduction and the structure of these molten mattes. An alternating-current circuit was used to eliminate the effect of any possible electrode reactions. Apparatus The Conductance Cell: Due to the high specific conductance of the systems studied (10' to 10" ohm-' cm-'), the classical two-terminal cell and Wheat-stone bridge apparatus could not be used. A four-terminal cell was developed in order to eliminate lead resistance, and an ac potentiometer circuit was designed to give rapid and sufficiently accurate measurements of the cell resistance. A diagram of the conductivity cell is given in Fig. 1. The molten matte is contained in a dense alundum crucible, and spectrographic graphite rods that dip into the molten matte serve as the four conductance terminals. Two of the graphite rods on opposite sides of the cell serve as current-carrying leads, and the other two graphite rods are null-current probes that detect the potential drop across the cell. These graphite rods are contained in silica tubes, and the lower constricted portions of the two silica tubes define the column of liquid whose electrical resistance is being measured. The electrical resistance of the broad ex-

Jan 1, 1956

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.' In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,' the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956

By T. M. Morris

A SEARCH of the literature reveals that no measurements have been made of the forces acting between a small solid particle whose surface is hydrophobic, and an air bubble to which the solid adheres, both immersed in water. Analyses have been made of the forces acting to support a greased solid on the surface of water, and the forces acting to cause a solid, whose surface is hydrophobic, to adhere to an air bubble in water. The latter analysis T. M. MORRIS, Junior Member AIME, is in the Department of Metallurgical Engineering and Mineral Dressing, School of Mines and Metallurgy, Rolla, Mo. New York Meeting, February 1950. TP 2734 B. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 16, 1949. This paper is the result of work done for part of a doctor's thesis at the Missouri School of Mines and Metallurgy. is often incomplete, however, because the internal pressure of the bubble has been neglected. It will be demonstrated that the internal gas pressure is not a negligible factor when dealing with bubbles of the size encountered in flotation. A study of the forces acting between an air bubble attached to a large flat surface is informative. It must be borne in mind, however, that this is not the condition present in a flotation cell, where the particle is small compared to the size of the bubble. The bubble is allowed to spread to its maximum contact angle on a large flat surface in the first case, whereas in the second case, the spread of the bubble is limited to the surface of the small particle which is presented to the bubble. Kabanov and Frumkinl studied the forces acting to cause adhesion of bubbles of hydrogen to a large surface of mercury, which served as an electrode in a dilute sulphuric acid solution. The force acting to hold the bubble to the mercury surface was found to be the vertical component of the surface tension between hydrogen and the sulphuric acid solution. The forces tending to cause the bubble to separate from the mercury surface were found to be: (1) the force exerted due to the internal pressure of the bubble acting upon the area of contact between the bubble and the mercury surface, and (2) the buoyant force of the bubble minus the hydrostatic force acting at the base of the bubble. These investigators photographed bubbles that were just on the verge of separating from the mercury surface. From these photographs, they measured the contact angle between the mercury surface and the tangent to the hydrogen-solution interface at the point of contact between bubble and mercury surface. They calculated the volume of the bubble and the internal pressure of the bubble. The equivalence between the upward acting and downward acting forces was remarkable. Wark2 pursued an investigation similar to that of Kabanov and Frumkin, and at the same time. His deductions verified those of Kabanov and Frumkin. He also considered the conditions present in flotation and was aware of the effect of the internal pressure of the bubble. Further, he proposed several conditions under which a small solid particle would adhere to an air bubble in water. In 1922, Edser," an English physicist, made the following statement. "It must be remembered that no particle could float stably, but for the possibility of variation of the contact angle, for if this were a constant, a slight tilt would inevitably cause the particle to sink." Wark criticized this statement, maintaining that the contact angle does not vary. The experimental data to be presented indicates that Edser was correct. Experimental Procedure: Briefly, the experimental procedure was as follows. A bubble of air was generated in distilled water. A rod of known diameter, one end of which was water repellent, was attached to this bubble. The weight of the 'rod was measured. The internal pressure of the bubble was measured with a manometer. The hydrostatic head from the surface of the water to the bottom of the rod was measured. The angle between the horizontal projection of the end of the rod and the tangent to the bubble at the circle of contact be-

Jan 1, 1951

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By A. Phillips, D. H. Killpatrick, V. Kerlins

The tensile failure of two dispersion-strengthened Ni-20 Cr alloys was studied and compared to the fracture of a similar alloy with no dispersoid. The fracture characteristics were studied using electron fruc-tography and transmission electron microscopy. In all three cases, the mode of failure was found to be microvoid coalescence. The failure in the dispersion-strengthened alloys was found to have initiated at the particles. The size of the dimples in the fracto-graphs was found to be related to the spacing of the particles, but not to the total elongation before failure. The elongation before failure was found to be related only to the amount of dispersed phase. These results are compared to those predicted by a theoretical model of ductile failure. THE continually increasing strength requirements for creep-resistant materials capable of long life at service temperatures above 1600"F (875"C) have developed considerable interest in dispersion-strengthened nickel-base alloys. The high yield strength of these alloys results from the presence of a dispersion of fine particles of thoria which act to impede the normal motion of dislocations. Many theories have been presented to explain the role of the dispersion in the strengthening of these alloys. A good review of these theories is presented by Ansell.' The ultimate strength of such alloys is not only related to mechanisms raising the yield strength, but also to the amount of work-hardening which occurs. This work-hardening is determined by the work-hardening rate and the amount of plastic strain before failure. Since fracture limits the amount of plastic strain, a study was undertaken to gain a better understanding of the fracture mechanisms in these alloys. Electron fractography and transmission electron microscopy were used to study the fracture characteristics in two dispersion-strengthened alloys and one similar alloy containing no dispersoid. These results are related to the tensile properties of the dispersion-strengthened alloys at room temperature and at 2000°F (1095°C). The results are also related to a theory for ductile fracture. 1) PROCEDURE Standard tensile specimens were made from 0.020-in. (0.051-cm) sheets of three different Ni-Cr alloys. The alloys had nominal compositions of Ni-20Cr, Ni-20Cr-2Th0,, and Ni-2OCr-4Th0,. All alloys were supplied in an annealed condition. The specimens were fractured in tension at room temperature to determine the effect of the dispersed thoria on the fracture appearance. The tensile properties were determined from the average of a minimum of three ten- sile specimens for each condition tested. The fracture surface of all of the alloys was examined by electron microscopy using standard two-stage plastic-carbon replica techniques. Thin foils of the dispersion-strengthened alloys were used to investigate the size and spacings of the dispersion particles, and to investigate sections of the 2 pct thoria alloy taken from areas of the specimen adjacent to the fracture surface. The thin foils were mechanically ground to 0.010 in. (0.025 cm) and then chemically polished to approximately 0.001 in. (0.003 cm) in a solution of 29 g of ferric chloride and 10 ml hydrochloric acid in a liter of water. The polishing solution was maintained at 150"F (65°C) during the thinning operation. The final thinning of the foil was done electrolytically using a solution of 700 ml ethanol, 100 ml 2-butoxy eth-anol, 120 ml distilled water, and 78 ml perchloric acid (70 pct). The potential was maintained at 15 v and the bath temperature at -20°~ (-29°C) during the thinning operation. The final thickness of the foil was approximately l000A as determined from the width of twins boundaries observed in many of the foils. 2) RESULTS AND DISCUSSION The electron fractographs of the fracture surfaces of the alloys are shown in Figs. 1, 2, and 3. The normal interpretation of this type of fractographz is that, as a result of the difference between elastic and plastic properties of the matrix and the particles or other inhomogeneities in the alloy, microvoids are formed

Jan 1, 1969

By S. Harries Daddow

IN order to get an idea as to the strength of steel rails, it will be well to review the tests to which iron rails have been subjected. In England, Mr. Ashcroft found that the best 80 pound rails broke under a 300 pound weight, falling 15 feet. In Germany the Society of Railway tyfanage1-s determined 011 and have long applied a test of 1000 pounds falling 101/2 feet, as the standard which all first-class iron rails must reach. In this country no inspection nor test is applied, but tests made show that iron rails fro; our most reliable makers, break under a G foot fall of a 1500 pound drop as an extreme test, most of those tested breaking under a far less test; some breaking with less than a 3 foot fall of the same weight. Everywhere where steel has been used, engineers have come to the conclusion that some test is required to show the regularity and strength of the product. As compared with iron, the tests which steel will stand are wonderful. After numerous experiments partially based on the experience of the rail-mill at Graz, belonging to the Southern Railway of Austria, the Society of German Railway Managers fixed upon a test of 2000 pounds falling 138 feet. They found that this test represented the steel which suited their necessities, and also found that with steel of otherwise average purity, this test represented about one-half per cent. of carbon, and made it a rule to take no steel containing under three-tenths of a per cent. of carbon, because it was too soft. They expressed a hope that a harder steel could soon be made tough enough to stand the same test. I n England, a test was adopted of 2240 pounds, falling 15 to 17 feet on the rail on heavy bearings. This test has been found satisfactory under heavy traffic on average road-beds, and has been invariablyPILLAR of coal, which are designed and left in our mines as the means of supporting the overlying strata of our coal-beds, and securing protection to the miner, are not only insufficient for these purposes, but the most objectionable means of providing the desired security to life and property. Though such pillars are left at a great sacrifice to the owners of collieries and mineral lands, loss to the resources of the commonwealth, and ultimate privation to the public, they defeat the very ends for which they are designed, and not only do not secure life and property, but are as fatal to the one as ruinous to the other. Propositions.-It is eminently desirable that the resources of the Common wealth-particularly our mineral wealth in anthracite coal, which is limited-should be carefully utilized and made available, not only to ourselves but our posterity. Yet, speaking as an anthracite miner, we are wasting our resources of coal with a recklessness which will bring ruin in the end, unless checked, not only to the iron manufacturing interests of the East, whose chief protection, in competition with the iron-masters of the interior, lies in a cheap and abundant supply of anthracite furnace fuel, but to the best interests of the State. It is, consequently, not only desirable, but necessary, that we should realize every ton of coal from each colliery, and every acre of coal area, in order that our resources may not be wasted at present, to breed want in the future, and to realize the greatest present benefit to the mine, the miner, and the public. It is not possible, however, to secure these ends, if we continue to leave, as we do at present, from one-third to one-half our resources in anthracite as pillars in our mines. But our sad bills of mortality, our abandoned collieries, and our yawning mountain-sides, present ample evidence that even this enormous waste of coal, though left for the purpose of protecting life and property, is as totally inade-

By D. G. Westlake

Alloys of poly crystalline Nb-H have been tensile tested at 77" and 120°K after slow-cooling and after quenching from room temperature. A rationale has been developed to explain the effect of cooling rate on ductility in terms of microstructure. The inferior ductility of the slow-cooled alloys in this temperature range can be attributed to the precipitation of coarse hydride particles that fracture in the early stages of plastic deformation. Quenching Produced much smaller hydride particles and a decreased tendency for initia-tion and popagation of cracks. Prismatic dislocation loops, punched into the matrix of quenched alloys, eliminate the yield point and may Play some role in the low temperature ductility of the quenched alloys. The difference in ductility between quenched and slow-cooled V-H alloys was even greater than that observed in the N b-H alloys. It is well known that the ductility of Nb-H and V-H alloys decreases with increasing hydrogen concentra-tion and with decreasing temperature.1-l1 The follow-ing are some of the numerous mechanisms that have been adopted in attempts to explain these observations: 1) hydrogen-dislocation interarction,4'6 2) lowering of the crack surface energy by adsorbed hydrogen,9'10 3) localized lowering of the niobium bond strength,9 and 4) exertion of pressure inside voids by molecular hydrogen.6 A recent study1' indicates that, in some way, the embrittlement is related to the precipitation of a hydrogen-rich phase, because embrittlement and hydrogen solubility have the same temperature dependence. Most of the investigators observed that at very low temperatures there was a return of the ductility. Thus, hydrogenated niobium and vanadium may be said to exhibit a low temperature ductility minimum."1'8'9 It has been reasoned by most observers that diffusion is required for the embrittlement mechanism to be operative, and that as hydrogen becomes immobile at very low temperatures, the ductility increases. This investigation of the mechanical behavior of Nb-H al-loys under various conditions is an attempt to gain a better understanding of the low temperature ductility minimum. EXPERIMENTAL Tensile specimens, with gage length dimensions 20 by 3 mm, were machined from sheet stock" and both faces were ground on wet 600 grit Sic paper to obtain a final thickness of 0.5 mm. Annealing as described earlier12 resulted in average grain diameters of 0.3 mm. The recrystallized niobium tensile specimens were electropolished in 90 parts H2S04, 10 parts HF (48.9 pct) by volume, at 287°K and 30 v. Hydrogen, which may have been present in the starting material and/or added during specimen preparation, was removed by annealing at 1073°K in a dynamic vacuum of 2 X 10-6 torr. Hydrogenated specimens (1.15 at. pct H) were prepared by reaction with a known quantity of pure hydrogen (obtained by thermal decomposition of UH3) at 1073oK, followed by cooling at the rate of 100" per hr. These were vacuum encapsulated, homogenized at 573°K for 3 to 5 hr, and furnace-cooled. Tensile tests were conducted on an Instron machine at a strain rate of 4 x l0-5 per sec. The gripping device was such that the specimen was positioned below the crosshead. Thus, subambient test temperatures could be obtained by immersion of the device in a cooling bath of either liquid nitrogen or Freon-12. The temperature of the Freon-12 was controlled within ± 0.1°K of the desired temperature by automatically monitoring the flow of liquid nitrogen through a copper coil in the bath. Slow-cooling to 77°K was accomplished as follows. The testing device was surrounded by a rubber jacket, open at the top and with small holes in the bottom. Liquid nitrogen, brought up to the bottom of the jacket, entered the holes and vaporized quickly. The temperature was monitored at the specimen with a copper-constantan thermocouple, and a constant cooling rate of 2 deg per min was easily achieved by controlling the level of the liquid nitrogen outside the jacket. RESULTS AND DISCUSSION Low Temperature Ductility Minimum. Resistometric studies of both Nb-H12 and V-H13 indicated that at tem-peratures less than 150°K, virtually all of the hydrogen

Jan 1, 1970

By C. P. Lawhon, J. P. Simpson, W. M. Evans

Recent efforts to design drilling fluids for increased drifting rates have confirmed some laboratory results of other investigators, but have also produced additional data that should be considered. These data were obtained under controlled test conditions using a microbit drilling machine. Clays and some polymers have previously been reported to cause reduction in drilling rate. Recent data have shown that under laboratory conditions, suspensions of a single day or polymer have sometimes given faster drilling rates than when water was used. Measurements have been made of clay suspensions and polymer suspensions comparing filtration (I) under API conditions, (2) while drilling with temperature of 150F and differential pressure of 1,000 psi and (3) under dynamic conditions after drilling. Some correlation between instanraneous filtration (white drilling) and drilling rate has been observed. INTRODUCTION Several papers have been presented that related drilling fluids to penetration rate. Generally, it was found that a decrease in the solids concentration resulted in significant increases in the drilling rate. Of course, this change also resulted in a decrease in the viscosity of the drilling fluid.' Conclusions from investigations by this laboratory are in agreement. Data have shown that of the simple mud measurements commonly made at the drilling rig (density, plastic viscosity. yield point, API filtrate and total solids), only the density and total solids have a significant relationship to the drilling rate in Berea sandstone when attempting to correlate a single mud property individually.' More recent drilling rate experiments have been designed to study (1) effects of individual clays and polymers on drilling rates in Berea sandstone and Lueders limestone, (2) the relationship between drilling rate and dynamic filtration as measured after drilling and (3) the relationship between drilling rate and dynamic filtration as measured during drilling. Data show that drilling rates are dependent upon type and concentration of particles, type of formation and filtration of the individual fluids while drilling. Mud pressure: pressure of drilling fluid as measured after leaving the drilling chamber (Fig. 1). This is taken to be approximately the mud pressure just past the bit and at the face of the formation. Terrastatic pressure: pressure representing weight of overburden. Formation pressure: pressure of formation fluid as measured at outlet of drilling chamber (Fig. 1). This is taken to be approximately the pressure of fluid in the interstices of the formation. Differential pressure: difference between the mud pressure and formation pressure. LABORATORY EQUIPMENT AND TESTING PROCEDURE The drilling equipment was described in two previous publications."' Main components are a drilling chamber, filter-heater, rotary drive and variable-speed circulating pump. Auxiliary pumps supply pressure boosts for the mud, terrastatic and formation pressures. All equipment is designed for 15,000 psi and 500F. Capacity of the circulating system is approximately 7 gal. The mechanical design was facilitated by moving the rock down onto the bit. Data collected with this design should not differ from that obtained by a normal design where the bit moves into the rock. Drilling fluid is pumped through 50 ft of ID pipe coiled in an oil bath, enters the rotary shaft at a right angle and is pumped through the jets on the bit (Fig. 1). Most of the drilled solids are extracted by a screen mounted in the circulating system on the suction side of the pump. Data reported in this paper were obtained by controlling these parameters: mud pressure, 5,000 psi; formation pressure, 4,000 psi; terrastatic pressure, 5,000 psi; force on bit, 1,000 Ib; formation, Berea sandstone and Lueders limestone; flow rate, 7 gal/rnin; bit, 11/4-in. diameter with two 0.078-in jets; mud temperature. 150F; and rotary speed, 60 rpm. Mud pressure was controlled at 5,000 psi, thus giving a differential pressure of 1,000 psi even though the fluid densities varied. Cores of 3%;-in. diameter and 8 in. long were selected from quarry blocks to provide some control of grain size distribution, permeability and porosity. A 2-in. section was cut off each core and a I -in. diameter plug was taken from this section. Permeability to 5 percent by weight sodium chloride solution was determined and the large cores were

By Arnulf Muan, D. P. Masse

PHASE relations in the system CoO-SiO2 have been determined as a basis for further investigations of thermodynamic properties of olivine solid solutions involving Co2SiO4 as a component. Previous data on the system CoO-SiO2 are incomplete or uncertain. Biltz and Lemke1 determined the melting point of cobalt orthosilicate as 1345°C , but Asanti and Kohlmeyer2 have later found a considerably higher temperature, 1420°C. The latter authors also studied melting relations of one mixture on the CO side and two mixtures on the SiO2 side of the orthosilicate composition and sketched a tentative phase diagram for a limited composition range of the system. However, no phase identification was carried out, and the authors left unanswered the question of the possible existence of a stable meta-silicate phase. Greig3 showed that a 90 wt pct SiO2-10 wt pct Co mixture at 1725°C consists of two immiscible liquid phases. The quenching technique was used in the present investigation. Mixtures of high-purity cobalt oxide ("Fisher Certified") and dehydrated silicic acid ("Baker Analyzed") were equilibrated in air atmosphere. The samples were then quenched to room temperature and the phases present were identified by microscopic and X-ray examination. The samples were kept in small envelopes made from thin (0.0004 in.) platinum foil. Thermodynamic data which have become available recently for Pt-Co alloys4 were used to check that the losses of COO from the oxide samples by alloying of cobalt with platinum in the present investigation were too small to change significantly the compositions of the oxide material during the equilibration. A vertical tube furnace with an 80 pct Pt 20 pct Rh resistance winding was used in runs up to 1510°C. Temperatures in these runs were measured with a Pt vs 90 pct Pt 10 pct Rh thermocouple calibrated against the melting point of diopside (CaMgSi2O6, 1391.5?C). The given temperatures as measured by this technique are estimated to be accurate to *5°C. Quench runs at temperatures above 1650°C were made with a modified Roberts and Morey5 strip furnace, using strip resistors composed of a 60 pct Pt-40 pct Rh alloy. Temperatures were measured with an optical pyrometer which was calibrated against the liquidus temperature of a mixture composed of 10 wt pct CaO, 90 wt pct SiO2 (1707°C). The temperatures measured with this technique have an estimated accuracy of +15°C. The results are shown graphically in Fig. 1. Only one intermediate phase, the orthosilicate Co2SiO4 with olivine-type structure, is stable in addition to the end members cobalt oxide and silica. The melting point of the orthosilicate was found to be 1415" ± 5°C. The metastilicate CoSiO3 is not stable at the temperatures of the present investigation. The two eutectic points in the system CoO-SiO2 where COO plus olivine, and olivine plus silica, coexist with liquid were found to be 72 wt pct COO and 1407°C and 63 wt pct COO and 1381°C, respectively. The melting point of cobalt oxide in air was taken as 1745?C, based on the previous data of Aukrust and Muan.6 Within limits of error (+ 5?C), identical eutectic temperatures to those determined in air were found when two representative mixtures were equilibrated at 1 atm O2 pressure and in an atmosphere of 84 vol pct CO2, 16 vol pct H2. This suggests that changes in oxidation state of cobalt in the condensed phases are not significant as far as their effect on the phase relations are concerned. This inference was substantiated by failure to detect7 any "excess oxygen" (i.e., oxygen in excess of that contained in Co2SiO4) in a sample of orthosilicate composition equilibrated in air 10°C above the liquidus temperature and subsequently quenched to room temperature. This work was carried out as part of a research program sponsored by the U.S. Atomic Energy Commission under Contract No. AT(30-1)-2781.

Jan 1, 1965

By T. M. Morris

A SEARCH of the literature reveals that no measurements have been made of the forces acting between a small solid particle whose surface is hydrophobic, and an air bubble to which the solid adheres, both immersed in water. Analyses have been made of the forces acting to support a greased solid on the surface of water, and the forces acting to cause a solid, whose surface is hydrophobic, to adhere to an air bubble in water. The latter analysis T. M. MORRIS, Junior Member AIME, is in the Department of Metallurgical Engineering and Mineral Dressing, School of Mines and Metallurgy, Rolla, Mo. New York Meeting, February 1950. TP 2734 B. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 16, 1949. This paper is the result of work done for part of a doctor's thesis at the Missouri School of Mines and Metallurgy. is often incomplete, however, because the internal pressure of the bubble has been neglected. It will be demonstrated that the internal gas pressure is not a negligible factor when dealing with bubbles of the size encountered in flotation. A study of the forces acting between an air bubble attached to a large flat surface is informative. It must be borne in mind, however, that this is not the condition present in a flotation cell, where the particle is small compared to the size of the bubble. The bubble is allowed to spread to its maximum contact angle on a large flat surface in the first case, whereas in the second case, the spread of the bubble is limited to the surface of the small particle which is presented to the bubble. Kabanov and Frumkinl studied the forces acting to cause adhesion of bubbles of hydrogen to a large surface of mercury, which served as an electrode in a dilute sulphuric acid solution. The force acting to hold the bubble to the mercury surface was found to be the vertical component of the surface tension between hydrogen and the sulphuric acid solution. The forces tending to cause the bubble to separate from the mercury surface were found to be: (1) the force exerted due to the internal pressure of the bubble acting upon the area of contact between the bubble and the mercury surface, and (2) the buoyant force of the bubble minus the hydrostatic force acting at the base of the bubble. These investigators photographed bubbles that were just on the verge of separating from the mercury surface. From these photographs, they measured the contact angle between the mercury surface and the tangent to the hydrogen-solution interface at the point of contact between bubble and mercury surface. They calculated the volume of the bubble and the internal pressure of the bubble. The equivalence between the upward acting and downward acting forces was remarkable. Wark2 pursued an investigation similar to that of Kabanov and Frumkin, and at the same time. His deductions verified those of Kabanov and Frumkin. He also considered the conditions present in flotation and was aware of the effect of the internal pressure of the bubble. Further, he proposed several conditions under which a small solid particle would adhere to an air bubble in water. In 1922, Edser," an English physicist, made the following statement. "It must be remembered that no particle could float stably, but for the possibility of variation of the contact angle, for if this were a constant, a slight tilt would inevitably cause the particle to sink." Wark criticized this statement, maintaining that the contact angle does not vary. The experimental data to be presented indicates that Edser was correct. Experimental Procedure: Briefly, the experimental procedure was as follows. A bubble of air was generated in distilled water. A rod of known diameter, one end of which was water repellent, was attached to this bubble. The weight of the 'rod was measured. The internal pressure of the bubble was measured with a manometer. The hydrostatic head from the surface of the water to the bottom of the rod was measured. The angle between the horizontal projection of the end of the rod and the tangent to the bubble at the circle of contact be-

Jan 1, 1951

By D. W. Mitchell

INE operators have a choice of several classi- fications of mechanical loaders. Within each classification there are many types and makes available. Table I lists loaders on which manufacturing data as to operating characteristics are available. This paper discusses the conditions met in a mine as they affect these characteristics. It is assumed that management will provide satisfactory engineering, supervision, power, maintenance, loader service within a concentration of workings, and a balanced working cycle served by balanced production equipment. These are factors which affect the optimum operational efficiency of a loader. The conditions which determine loader choice are: Height of Vein—The main limitation to the use of a loading machine is the height to which the vein is mined; i.e. a loader cannot be higher than the place in which it is to work unless rock is taken. Since there are several low vein loaders being developed and successfully applied, this does not appear to be a requisite of an efficient mining operation. The maximum useable height of a loader should be equal to the working seam thickness less a working clearance for travel and operation. A—Working seam thickness = B—Artificial roof support thickness = C—Safe headroom below support = (generally about 6 in.) D—Height of roadway = E—Total of B + C f D =_______________________ A—E = maximum loader height F—Distance from top of roadway to bottom of roof support = G—-Height of loader's coal or ore line (see Table I) = H—Difference between F and G = Size of largest broken particle + a safety factor of 2 to 3 in. H is a loadability factor and is important because the clearance over the top of the conveyor chain to the roof or roof support must be greater than the largest broken particle or else the particle and/or the conveyor chain may be broken. From this standpoint it might be desirable to use a lower height machine even though it may have a smaller capacity, though this is warranted only when increased lump realization offsets lower man-day and machine pro- duction rates. Ivan Given has stated, "Loading should not be handicapped by securing lump only to grind it in the breaker." Width of Working Place—The width of a working place is the greatest width a place may be safely driven. The working place includes not only the face but the roads the loader must tram when mucking out more than one face. The width is limited by the system of placing props with sufficient room between them for the machine runner (about 2 ft). Maximum width of place in which the loader will operate at maximum efficiency is determined by the type of mounting. With track-mounted loaders, maximum width of place is determined by maximum angular swing of the loading head and proximity of track to the face. The use of double track leads to added expense and operational complexities. Several mines that have used double-track systems have found that a substantial saving is made by the use of machines that load out wider places. Trackless loaders may work in rooms of any maximum width. Minimum width of place in which a loader will operate is determined by width of the loader plus a safe movement area for the operator. Often a barodynamic study of the mine will show that either an increase in room width and/or a change in the system of propping may be made by using roof bolting, full or part-width room timbers, removable aluminum I-beams at the face, etc. Increasing the width of a working place will, in general, increase loader operating efficiency by providing more material per fall and by decreasing the preparation and moving time per ton. A change in the system of propping that would increase the minimum width might permit the use of a higher capacity loader with safer working conditions. Proper face tirnbering is necessary to insure safety from roof falls and because the speed of preparation and loading generally increases since the men work with greater assurance and there is less chance of kicking out posts. Maximum Room Length—With the exception of the scraper and the duckbill, the limit to room

Jan 1, 1952

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.'-' This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,' by the copper-decoration technique,' by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18'19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By M. Bevis, E. O. Fearon, P. C. Rowlands

Fe-Ni and Fe-Ni-C martensite specimens have been deformed in compression at room temperature and the habit planes of operative deformation twins determined by two-surface optical trace analysis. The full orientations of the martensite crystals were determined from divergent X-ray beam diffraction patterns. The experimental results are in excelled agreement with predicted twinning modes. In particular, the habit planes of some deformation twins in bcc martensites are consistent with a "Type XI compound'' twinning mode with Kl, Kz, 71, 77~ elements given by {5, 8, 11) {ioi}, (33) (ill) Tetragonal derivatives of this mode are operative in bct martensites. UnUSUAL deformation twinning modes have been reported by Richman' to occur in Fe-Ni-C martensites with bcc and bct structures. The twin habit planes were determined by single-surface trace analysis (pole locus method) and the remaining twinning elements were determined from the geometry of twin-twin intersections. The indices assigned to the observed habit planes are (3 101, "(089)" and "{0, 1,13)" or "{1,2,7} ", and only in the first case do the twinning elements correspond to a predicted twinning mode. This is mode 1.4 in the paper by Bevis et al. The results presented in Ref. 2 indicate that previously unpublished bcc and bct modes should be operative in preference to the (130) mode and anomalous modes reported by Richman. In view of these results and the uncertainties involved in determining habit planes from single-surface trace analysis and twinning elements from twin-twin intersections5 a two-surface trace analysis of deformation twins in Fe-Ni and Fe-Ni-C martensites has been carried out. EXPERIMENTAL PROCEDURES Two alloys with compositions Fe-23 pct Ni-0.6 pct C and Fe-30.4 pct Ni were prepared from 4N pure materials by induction melting under a vacuum of 10"5 mm Hg. The alloys were homogenized at 1350'~ for 5 days. Both of these alloys are austenitic at room temperature with M, temperature - — 50"C. The aus-tenite grain size of the Fe-Ni-C alloy was approximately 300 to 400 p. The Fe-Ni alloy was remelted in a vertical tube furnace and the melt lowered slowly from the hot zone of the furnace to produce s ingle -crystal austenite specimens. Specimens approximately 10 by 5 by 5 mm were cut from the ingots and quenched to various temperatures below the Ms temperature. The specimens were elec-tropolished in a 10 pct perchloric acetic electrolyte before being deformed in compression at room temperature. Martensite plates which exhibited profuse deformation twinning were selected for analysis and the specimen polished on a second surface such that the two surfaces which contained the martensite plate enclosed an obtuse angle of approximately 145 deg. The specimens were then electropolished to reveal the traces of the deformation twins on both surfaces. The full orientations of the martensite crystals were determined using a divergent X-ray beam technique (Kossel line technique) employing an AEI SEM2 electron probe microanalyzer. Details of this technique which include a detailed description of the Kossel camera attachment to the microanalyzer used in the present experiments have been discussed elsewhere.3 Only additional details relevant to this investigation are discussed here. The specimens were mounted with one surface normal to the incident electron beam as illustrated schematically in Fig. 1. The martensite plates to be analyzed were located using the normal scanning equipment of the microanalyzer. The position of the electron beam and hence the position of the source of divergent X-rays generated within the crystal could be located to within 1 p. Exposure times of approximately 8 to 10 min were required for back-reflection Kossel patterns and it was found that useful diffraction patterns could be obtained consistently from heavily deformed martensite plates. A reference line (carbon contamination mark) produced on the two surfaces of the specimen by scanning the electron beam in a direction having a known relationship with the reference !ine in the X-ray camera enabled the full orientation of the crystals to be determined. Martensite plates with widths as small as 8 p could be oriented using this procedure. The Kossel line patterns were interpreted using the charts developed by Rowlands and ~evis~ as generally

Jan 1, 1969

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,' Streicher,' and Mc Nutt' that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,' Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,' Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3'8'9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By R. D. Russell, R. M. Farquhar

SOTOPIC tracers have become an important aid in following the progress of chemical processes in the laboratory. It has recently been found possible to utilize a system of naturally existing iso-topic tracers to obtain information about the geological history of lead ores. Common lead, such as is found in lead deposits, is a mixture of four stable isotopes having atomic weights 204, 206, 207, and 208. Of these, the last three are identical with the lead isotopes produced as stable end products of the radioactive decays of uranium and thorium: the first, lead-204, is not known to be produced on the surface of the earth by any process. Since uranium and thorium Occur in the surface regions of the earth in amounts comparable with lead, and since the half-lives of uranium and thorium isotopes are of the same order as the age of the earth, they produce the radiogenic lead isotopes in amounts comparable to the amount of nonradiogenic lead present. Every significant exposure of a sample of lead to uranium and thorium will therefore lead to the permanent alteration of the lead isotope ratios in that sample. It is this unique property of lead that serves as a means of tracing the history of a lead sample in terms of its contacts with the radioactive elements. If lead from a lead mineral has been analyzed with a mass spectrometer, the measured isotope ratios are determined entirely by the isotope ratios of primeval lead, which are identical for all minerals, and by the particular history of the sample. It follows that for samples from any particular geological area, observed differences in the isotopic composition are enough to distinguish different geological histories. An illustration of the qualitative application of this statement is given in Table I by analyses of some galenas from the western Cordillera. Samples from deposits in Pre-Cambrian sediments have very different lead isotope ratios from those of the ores in the Paleozoic sediments. Although the two types are associated closely geographically, it is apparent that they have had quite different histories and have probably been emplaced at quite different times, as the ideas outlined in the following section suggest. Even when applied quantitatively, a lead isotope analysis can never indicate a unique history of any lead sample. However, it greatly restricts the choices available and combined with other geological and geochemical data can lead to a much better understanding of the genesis of lead ores. General Character of Lead Isotope Variations: Early isotopic analyses of common leads by Nierl showed that geologically younger leads were generally richer in isotopes of masses 206, 207, and 208, with respect to that of mass 204. This regularity of measured lead isotope ratios can be easily observed by plotting each of the ratios Pb207/Pbm and Pb205/ Pb204 against the ratio Pb206/Pb204. In both graphs the points lie scattered closely about a well defined mean curve. It was immediately supposed that this regularity resulted from the growth of all leads from a common primeval lead present at some time, To, early in the earth's history. Lead in the outer part of the earth would become continually enriched in the radiogenic isotopes as a result of the uranium and thorium intimately associated with it. The subsequent extraction of some of this lead and formation of a lead mineral free of the radioactive parents provide samples of lead existing in the earth at the time of mineralization, T. Younger leads in general will be richer in the radiogenic isotopes because they have been associated with uranium and thorium for a longer time. Then lead ratios would be given by the formulae: (Pb206/Pb204)YTPb^/Pb204) +f "(u201) kdt T (Pb207Pb204)r = (Pb208/Pb204)T0 + J (U295/Pb204) k' dt T (Pb208/Pb204) t = (Pb208Pb204 + J (Th204) A." dt [1] where A, A', and A" are the decay constants of U238, U285 and Th232. Summaries of measurements of radioactivity of surface rocks, such as given by Faul,2 are of limited

Jan 1, 1958

By Edward Hanrahan

September 1981 I'm here today to report on a revolution -- a revolution in the way the Federal Government looks at energy. I'm not talking about a simple change in the relative emphasis on sources -- such as more recognition for coal and nuclear power, with less rhetoric about "soft- technology." Nor am I describing a mere change in focus -- from the demand side to the supply side. And I am not referring exclusively to our obvious goal of budget cuts. No, I'm here to discuss a fundamental change in Federal direction -- one that started as soon as President Reagan was inaugurated, and one that is articulated in the National Energy Policy Plan he sent to Congress in July. That brief policy document was backed up by three volumes of supporting data; but I think I can catch it's flavor for you in just three phrases: * First, various energy forms complete with each other and complement one another. * Second, fair competition among them (which includes honest pricing) will give us the best "energy mix." • And, finally there may be ligitimate arguments about where Federal responsibility in regard to energy spills over into Federal interference; but it's about time we drew the distinction -- and eliminated the latter. This Administration's national energy policy is quite different from any we have had in recent years. It is tuned to human nature and changing times. We are seeking the best practical solutions in the energy -a lot better than the ones we have been offered before, but still something less than perfection. One way we do that is by counting on a fully informed public to guide it's own destiny. And, instead of treating energy as an isolated entity, we recognize it as part of the overall economy. The President's Program for Economic Recovery is as much a factor in energy policy as the specific actions of the Department of Energy. One striking difference from the past energy policy 1s that this policy plan does not say: "In 1985 we will -produce so many hundreds of millions of tons of coal: . . . or . . . "By the end of this century the Nation will be deriving X percent of it's electricity from wind generators." Unfortunately, targets like these are what many people have come to expect from the Federal Government -- and what they think of as energy policy, whether the figures hold up in the long run or not. But . . . think about it! Nether the Department of Energy nor any other part of the Federal Government produces coal, or mines uranium, or manufactures solar collectors. There are only a few sections of the country where the Federal Government generates and sells electricity. So it does not take any great insight to recognize that the amount of energy we will produce or consume as a Nation In the future depends on many factors beyond direct government action. And those future totals cannot be predicted precisely, anyway -- by the Government or by anybody else. According to our way of thinking, the choices should be up to the people. When the free market works within a healthy economy, individuals express their preferences in the marketplace -- adjusting the balance of all energy factors continually in a way that no computer could be programmed to reflect perfectly. So, instead of having the Government issue a rigid set of numerical goals, our main concern simply is that there be enough energy. We want the Nation itself to decide how much that should be, what form it should take, and how that energy should reach consumers. The marketplace decides. Considering the recent past, this is indeed a revolutionary idea. It has some pitfalls, and we won't reach this ideal of free choice overnight. But that is where we are headed. And I'll offer some evidence in a few minutes that the policy has already started working. First, let me give you some of it's highlights: 1) Nobody who appreciates the philosophical underpinnings of this Administration will be surprised that the energy policy shows faith In domestic energy production and the supply side of the economy; but it also recognizes the important role of energy conservation -- the wise and efficient use of energy resources.

Jan 1, 1982

By David S. Bolin

INTRODUCTION This paper is directed toward those companies or individuals who may be considering the possibility of tin exploration or development projects in South America. Although tin deposits are known in many countries of Latin-America including Argentina, Peru, and Mexico, the majority of the deposits are located in Bolivia and Brazil. These two countries also account for virtually all the current production. Many factors affect the economic decisions related to mining and exploration projects in this region including the following: 1) Types of deposits 2) Anticipated size and grade of deposits 3) Deposit geometry and ore distribution as it affects the selection of a mining method 4) Metallurgical amenability 5) Governmental policies 6) Taxation 7) Anticipated capital and operating costs 8) Marketing costs This discussion will be directed toward each of these points. The majority of the presentation will be concentrated on Bolivia as this country is the principal producer in the region, however, the potential for further tin development in Brazil is excellent. Due to the remote and previously almost inaccessible location of the stanniferous districts of Brazil, little is known with respect to size and type of non-alluvial deposits which may exist in this vast country. TYPES OF DEPOSITS Two major types of deposits are currently being exploited in Bolivia; alluvial, and hard rock or lode deposits. Bolivia produces substantial tin from both types of deposit whereas virtually all Brazilian production to date has been from alluvial sources. Alluvial Deposits Brazil: The alluvial tin deposits of Brazil are located in river channels and flood plains adjacent to low mountain ranges. The terrain containing the tin placers is flat, marshy, and generally jungle covered. The major controls of alluvial cassiterite concentration are the ancient and present stream channels. The average tin concentration in the placers varies from 500 grams to approximately 1.0 kilograms per cubic meter. Tin reserves in the Rondonia field of Brazil have been estimated at 600,000 tons of fine tin. A bucketwheel suction dredge went into production in the Rondonia district in 1979, and four others have since been ordered. Several other gravel pump, and hand mining operations are also in production in this field. In addition to the Rondonia district, tin occurrences are known from Xingu, in Para state, and in the state of Minas Gerais. Bolivia: The alluvial deposits of Bolivia are somewhat more complex due to the variable geomorphology and abrupt topography. Conventional placer accumulations of cassiterite are found in many stream channels and intermontane basins surrounding the major lode tin producing regions. In addition to stream and valley placers, a group of deposits locally referred to as "Pallacos" or "Llamperas" which consist of colluvium, landslide debris and glacial moraine material, contain substantial tin reserves in some areas. The stream channel and intermontane basins contain the only deposits which are presently being exploited by mechanized methods. One dredge is working the stream channel below Cerro Rico de Potosi and another is operating in an intermontane basin southeast of the city of Oruro. Both of these dredges are operated by private companies. The average grade for these operations varies from 250 to 500 grams per cubic meter. The largest of the intermontane basin placers known at present is the Centenario deposit located adjacent to the Catavi lode deposit. This deposit contains approximately 170 million cubic meters of material with an average grade of about 150 grams per cubic meter. The "Pallacos" deposits are found on the slopes of mineralized areas and in glacial moraine. The mineralized material is generally completely unsorted, with tin and sometimes tungsten values distributed erratically throughout the entire mass. Most of these deposits are worked by small leasors or cooperatives; however, at least one mechanized washing plant is in operation southeast of Oruro. The size of these deposits may reach up to several million cubic yards. Grades are very erratic, but may range from 200 to 500 grams per cubic yard. In addition to the formal mining operations, virtually every drainage surrounding the major mines is being worked by independent' miners utilizing hand mining and jig or pan concentration. The aggregate production from these operations is substantial. The

Jan 1, 1982