Search Documents

By E. A. Gulbransen, A. Pebler

Pressure-composition isotherms have been determinedfor the systems ZrMo2 -H2 between 0" and 900°C at hydrogen pressures between 10-4 and 760 Torr. Tkese studies plus X-ray diffraction analyses of selected compositions show that these intermetallic compounds form a complete series of hydrogen solid solutions within this temperature and pressure range. The partial molar enthalpies and entropies of solution of hydrogen in the three intermetallic compounds were calculated. The solubility of hydrogen in these Laves phases can be related to their free electron concentration. ThE reaction of hydrogen with inter metallic compounds of zirconium with Laves phase-type structure has both theoretical and practical interest. The in-termetallic compounds have structures different from any of the pure metals. In addition the electron to atom ratio of the intermetallics varies appreciably. In the nuclear materials field, these materials are of interest since intermetallic compounds may exist as precipitates in commercial zirconium alloys with transition metals. From studies on the hydrogen reaction, one can establish the stability of the intermetallic compounds relative to the hydrides of the component metals. The intermetallic compounds may also be used as getters for hydrogen and as materials for hydrogen storage. This paper will present the results of equilibrium and structural investigations of the ZrCr2-H2, the ZrV2-H2, and the ZrMo2-H2 systems for the temperature range of 0" to 900°C and the pressure range of Torr to 1 atm. A complete thermochemical analysis will be made of the measurements. Some of the results have been referred to in a survey paper' covering the types of hydrogen behavior observed in zirconium alloys. LITERATURE ZrCr2 is the only intermetallic phase in the Zr-Cr system.' It exists in two allotropic modifications. Between 900" and 1000°C the hexagonal MgZa (C14) structure transforms into the cubic MgCu2 (C15) structure. Beck4 has previously shown that the intermetallic ZrCrz takes up hydrogen into solid solution up to a composition H/ZrCr2 = 1.14 at room temperature and 1 atm hydrogen. A ZrCr2 hydride was stated to have a fcc structure. The binary Zr-V system has been investigated by williams5 although Rostoker and Yamamoto 6 had given earlier a partial phase diagram. ZrV2 was the only intermediate phase found in the system. wallbaum7 reported earlier that the compound ZrV2 hp the MgZm (CJ4) type structure with a = 5.288A and c = 8.664A. This was not comfirmed by Elliot8 nor by Matthias, Compton, and corenzwit9 who reported that ZrV2 has a cubic MgCua LC15) type structure. The latter authors gave a = 7.429A. Also, several authors do not agree on the temperature of the peri-tectic horizontal. It appears that ZrV2 may exist in several modifications. A high capacity for occluding hydrogen was reported by Beck4 who found H/ZrV2 = 1.38 at room temperature and 1 atm of hydrogen. ZrMoz is the only intermetallic phase in the Zr-Mo system.10 ZrMoa is formed by a peritectic reaction of the melt with a molybdenum-rich solid solution. ZrMo2 has the C15-type structure with a = 7.59A. MATERIALS High-purity chromium, vanadium, and molybdenum were used together with grade 1 crystal bar zirconium to prepare the alloys. Table I lists the chemical analysis and the sources for the metals. Ten-gram alloy compacts were levitated and melted in an inert argon

Jan 1, 1968

By H. O. Hofman

THE leading antimony mineral is stibnite. In smelting stibnite ore two processes are available, precipitation and roasting-reduction. The former is suited only for high-grade ores. As low-grade ores are more common than high-grade, roasting-reduction is of greater importance than precipitation. In the roasting process the aim may be to leave the oxidized antimony in the ore, or it may be to volatilize as much of the antimony as possible, collect the volatilized oxide as a rich intermediary product and smelt it for antimony, leaving the gangue poor enough to be considered a waste product. Whichever way the roast is conducted certain difficulties inherent in stibnite are encountered. These are: 1. The low melting point of stibnite which; according to Pelabon,1 is 550°C., according to Wagemann2 540°C., and according to Borgström3 546°C. 2. The ignition temperature: According to Friedrich,4 stibnite, if heated in air, begins to oxidize at 290°C. if the size of a grain is 0.1 mm. in diameter; at 343°, if 0.1 to 0.2 mm.; and 430° if 0.2 mm. 3. The fusibility of a mixture of Sb2S3 and Sb203 which in the form of kermesite (Sb2S3)2.Sb203 melts at 517°C.5 4. The volatility of Sb2S3 and Sb203, for which no numerical data appear to exist, although practical experience has shown that they are volatile at low temperatures.

Jan 1, 1916

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

Jan 1, 1923

By R. A. L. Black, J. E. Jennings

The problems of slope stability in open cast mines are examined. A criterion, the instantaneous stripping ratio, is suggested for use in the design of pit slopes and as an index of control at all stages of the exploitation of the orebody. This criterion may also be related to safety and to the maximizing of profits. Two approaches to safe design of slopes, one from the point of view of soil mechanics and the other from the point of view of rock mechanics, are described and critically compared. The effect on slope stability of the regional tectonic stress field is discussed. Explanation is given of the application of the Terzaghi effective stress concept to problems in both soil and rock environments, including possible effects when borehole deformation techniques are used to measure stresses in rock in situ. A company embarking on open cast mining is faced with two basic questions: 1) will the venture be profitable and 2) can it be carried out with safety? The two questions are obviously interrelated because both depend upon the slope angles adopted for the pit. The cost of open cast mining depends largely upon the stripping ratio, defined as the volume of overburden that must be removed to the volume of ore recovered. The steeper the slope angles, the more favorable the stripping ratio, but the stability of the slopes, and therefore the safety of men and materials in the pit, require that the angles be made relatively flat. Consequently, the design depends upon a compromise: the slopes must be steep enough to result in economical mining and flat enough to ensure safety. Today there is a world trend towards deeper mining by open cast methods. This is mainly due to the higher cost of underground mining and the lower cost of open excavation resulting from the introduction of large modern earth and rock-moving machinery. Deeper open cast mining has led to a very great increase in the volumes of wasted overburden, and much thought is being given to the considerable economic benefits which would result if pit slopes could be made steeper by even one or two degrees. The result has been an increasing interest in research into slope stability problems in the expectation that the application of scientific principles will provide solutions leading both to economies and to more predictable operation of the mines. In at least four places, the U.S., Australia, Western Germany and Southern Africa, comprehensive investigations are at present in progress, and it is the object of this paper to review some of the more important aspects of these programs. RELATION BETWEEN ECONOMY OF OPERATION AND SLOPE ANGLES The main object of any industrial enterprise in a free economy is to make a profit. In mining, where profits must be made from a wasting capital asset, a further definition of the profit motive is imposed, namely that the economic aim should be to maximize the total possible profit. But since profits deferred for a number of years are not as valuable as profits that are immediately available, it is usual to discount deferred profits at some rate of interest which reflects their current or present value in the hands of the investor. Thus, in mining the logical aim can be defined more closely still: to maximize the present value of the total future profits. In commercial terms the present value represents the market value of the operation as a going concern. Many factors enter into the forecast of current and future profits. They include the volume of production, the price of the salable product and the cost of production. Current profits can be estimated with reasonable accuracy by the operating engineers; but it is the task of economists and management to assess future trends in the mineral markets and in the economy as a whole, and together with the engineers, they can then estimate the future cost and profitability of the mining operations. In open cast mining, the rate of ore production once decided on remains a virtually constant factor unless a major change in the capital structure of the mine is made. But one factor over which the operator has a considerable measure of control is the ratio of the volume of ore mined to the volume of waste over-

Jan 1, 1963

By A. K. Mukherjee, J. E. Dorn

A modified Peierls model is Presented for the rationalization of the asymmetric plastic behavior of single crystals of bcc metals. The model assumes that the asymmetry of slip arises from a tendency toward asymnetric splitting of the a/2[111] screw dislocation. The approach differs from former theories however insofar as it assumes that the splitting is so minor ttut only the core energy is modified and that no real partial dislocations exist. As a consequence, the concepts of a line energy of a partial dislocation, interaction between partial dislocations, constriction energies, and stacking fault energies are not invoked. Instead the present analysis is based on a specialization of the Peierls mechanism which assumes an asymmetric dislocation core which is modified by the effective stress and permits cross slip. The theoretical predictions on the stress-temperature -strain rate and orientation relationship agree qualitatively with the limited experimental data that are currently available. Additional experimental work over wider ranges of conditions is suggested to provide more complete evaluation of the possible validity of this theory. RECENT experimental investigations on the low-temperature thermally activated deformation of bcc metals have confirmed the existence of several unique orientation effects. These will be described with the aid of the standard stereographic projection shown in Fig. 1. If slip were determined exclusively by crystal symmetry, the deformation characteristics would be symmetrical about X; = 0 and independent of whether the specimen were subjected to a tension or a compression stress, regardless of what combinations of slip planes might be operative. Experiments, however, reveal that neither of these symmetry based predictions are valid. A schematic representation of the commonly observed asymmetry of both the yield stress and the plane of slip is shown in Fig. 2. A reversal of the direction of stressing results in an inversion of the asvmmetric behavior. 1) Asymmetry bf Yielding. A detailed investigation on the asymmetric yielding in an Fe-2.7 pct Si alloy was repoEted by Tabka, Tikeuchi, and Furubayashi,1 Similar trends have been observed by Keh and Nakada on iron,' Stein on molybdenum,3 Bowen, Christian, and Taylor4 on columbium, Sherwood, Guiu, Kim, and pratt5 on Ta, Cb, and Mo. The degree of asymmetry not only depends on the atomic number and alloying but, in all cases that have been examined, it also increases with a decrease in the test temperature. 2) Asymmetry of the Slip Plane. Asymmetric $I-~: curves of the type shown in Fig. 2 have been found for several Fe-Si alloys6-8,1 and columbium.4 There is general agre_ement that near X: = 30 deg slip occurs by the [111](211) mode so that ?1 = 30 deg. As X; decreases it appears that [111](211) to [111](101) cross slip takes place leading to slip band traces on intermediate planes. And as xi approaches 0 deg, sharp

Jan 1, 1970

By Raymond Ward

Jan 1, 1945

By Charles T. Baroch, Charles J. Baroch

Nuclear energy probably has greater potentialities for changing the world's way of life than any other recent discovery. The atomic-bomb bursts over Hiroshima and Nagasaki suddenly changed the concepts of war. Peaceful uses of nuclear energy are advancing so rapidly that no study of economic trends is complete without giving them consideration. The minerals specialist, especially, must be aware of this new force in our lives, as minerals and metals are essential in harnessing the new force, and atomic energy itself is rapidly improving its competitive position in the energy field. Future historians may chronicle December 2, 1942, as the beginning of the Atomic Age. On that day Enrico Fermi and his co-workers at the University of Chicago produced and controlled the first self-sustaining nuclear chain reaction. Lie many inventions, the first application of nuclear energy was as a weapon of war. However, its potential usefulness in man's work and welfare far outweighs in economic importance its destructive use in war, unless its military effect would be considered so great and all-embracing that no major power will hereafter chance a world conflict. Recognition of this potential has generated a vast international effort to exploit the atom for peaceful beneficent purposes. Like its physical manifestation, the advent of nuclear energy has unleashed chain reactions that have pervaded the political, social, and economic environments of the world. The impact of nuclear developments in one of many fields is exemplified by the uranium mining industry. Uranium was discovered in 1789 and in the next century and a half it found only an insignificant use as a ceramic coloring agent; in fact, in the latter part of that period, it was a largely unsalable by-product of the radium and vanadium industries. Up to 1940 the total quantity of uranium metal produced was not more than a few grams, of doubtful purity. Thus the production of 12,400 pounds of pure

Jan 1, 1964

By C. L. Meyers, A. V. Levy, G. Y. Onoda, R. J. Kotfila

This paper presents the hypothesis that solid-solution hardening of regions in the order of tens of angstroms thick along grain boundaries is the most important mechanism controlling the ductile -brittle transition behavior of poly crystalline bcc refractory metals. Further, a physical model is developed and a general equation is derived to describe the dependence of the solute concentration at grain boundaries on temperature, nominal impurity concentration, thermal treatments, vain size, and prior plastic deformation. Analytical curves of the solute concentration at grain boundaries us temperature, calculated by means of the derived equation, are found to have the same general form as curves of ductility us temperature plotted from experimental data. Senziquantitative relationships between the transition temperature and metallurgical variables can he determined by using the physical model. The room-temperature brittleness of the poly-crystalline refractory metals (tungsten, molybdenum, and chromium) is a result of their high ductile-brittle transition temperatures. Recently studies on single crystals have revealed that, when sufficiently pure, these crystals have much lower transition temperatures than polycrystalline specimens of similar purity.'-3 For example, the transition temperature (measured by reduction in area in tensile tests) for very high-purity tungsten crystals has been reported to be as low as -50°F whereas polycrystalline specimens of similar purity had a transition temperature near 400" ~.' These results suggest that the ductile-brittle transition behavior of these polycrystalline metals can be attributed principally to the influence of grain boundaries on plastic flow and fracture. This paper contains a discussion of the manner in which grain boundaries influence the ductility of the poly-.crystalline bcc refractory metals and proposes that the segregation of impurities to grain boundaries is the most important mechanism for controlling the ductile-brittle transition behavior of these metals. Further, this paper contains an analysis of the effect of the compositional and structural variables on the grain boundary-ductility relationship, and introduces a semiquantitative model that can provide a foundation for more theoretical treatment to describe the influence of these variables on ductile-brittle transition behavior. PHYSICAL MODEL FOR PREDICTING DUCTILE-BRITTLE TRANSITION BEHAVIOR Grain Boundary Segregation of Impurities. Based on their own observations and on theoretical grounds, numerous investigators have suggested that impurities segregate to the grain boundaries. Such segregation would be expected because regions exist where both large and small foreign atoms fit with less strain than within the undistorted crystal structure. Therefore, the concentration of impurities should be higher at boundaries than within the grain body. TO estimate the degree (i.e., the ratio of grain boundary to nominal bulk concentration) to which an interstitial solute tends to segregate at boundaries within a solvent metal, the solubility rather than the size misfit could be used as a guide because solubility expresses the joint effect of both elastic and electronic factors.5 The solubilities of interstitial elements such as carbon, hydrogen, nitrogen, and oxygen are low in the group V-A metals and very low in the group VI-A metals.6 These low solubilities suggest that segregation to grain boundaries should occur for each of these solutes in both refractory metal groups. The difference between the ductility of single-crystal and polycrystalline bcc refractory metals can be described in terms of two distinct effects.4 The first of these is the general observation that grain boundaries hinder slip within grains and slip transfer between grains, and the second is that deformation is more complex in each grain of a polycrystalline specimen than it is in a single crystal. Mc Lean has pointed out, furthermore, that strong slip-hindrance effects at grain boundaries should occur in metals having strong segregation of impurities to grain boundaries. Therefore, the effect of grain boundaries on the hindrance of slip is expected to be the dominating influence on the ductile-brittle transition behavior of these polycrystalline refractory metals. cahn5 has suggested that temperature and solute mobility should influence solute equilibrium segregation at grain boundaries, and Fig. 1 illustrates

Jan 1, 1965

By D. E. Hawk, R. F. Burdyn, F. D. Patchen

Earlier work on a mud separator for barite recovery is extended to the design and construct ion of a rugged field unit. Problems associated with scale-up for field use include the me of dilution water and its effect on capacity, power requirements and pressures developed. Equations for these quantities are derived and applied in maximizing the beneficial effects of dilution and minimizing the power required. Tests on the full-size rotor show that its performance can be predicted by theory. The completed unit is compact and lighter than current decanting types. Its capacity is from 10 to 22 gal/min with corresponding barite recovery efficiencies of 92 to 86 per cent. INTRODUC'TION In an earlier publication a new type of centrifugal device was described for solid-liquid separations.l In that paper an operating equation was derived, and its validity demonstrated in laboratory scale experimentation. Some of the features apparent in this new device seem particularly well suited to the conservation of barite in field drilling-mud systems, hence the development was extended to the design and construction of a field unit. In the present paper the design problems associated with scale-up are considered. A full-scale, rugged self-contained field unit is described, and test results discussed which verify that the performance of the large field unit can be described by a simple operating equation. PRINCIPLE OF OPERATION OF SEPARATOR In principle, the new device is simply a perforated cylinder rotating within a body of fluid which is contained within a stationary case, as in Fig. 1. The frictional drag generated by the rotating cylinder causes part of the fluid to rotate. At the surface of the cylinder, assuming no slip occurs, the angular velocity of fluid and of the cylinder are identical. If there are suspended particles present of greater density than the fluid, the centrifugal force acting on these particles causes them to move radially away from the cylinder at some velocity vp . Where the Stokes settling equation holds, this velocity may be expressed as:2 d2 ?p rw2 If the case is provided with openings at both ends, a suspension can be pumped in at one end at a fixed rate. Part of the suspension can then be removed at a fixed rate at the other end of the case as underflow, and the remainder forced through the perforations and hollow shaft of the rotor to appear as effluent, also at a fixed rate. The radial component of the flow velocity of this stream as it reaches the rotor surface, is simply effluent flow rate divided by cylindrical surface area: Because up is a function of particle size, for some particular particle size, the velocities vp and v, will be equal in magnitude. This is defined as the critical particle size and represents the size above which all particles appear in the underflow and below which all particles appear in the effluent. For this equilibrium condition at the rotor surface, Eqs. 1 and 2 combined give

Jan 1, 1966

By Edward Walsh

In the early history of the production of metallic iron from the native oxides or ores, success attended the labors of the workman according to the care he devoted to his work, and according to the degree of skill he possessed in furnishing the required amounts of fuel and ores to be acted upon by the blast propelled by the bellows, trompe, or wooden tub, and delivered into the hearths of the Persian, bloomery, or Catalan forges. The same skill may also have been of avail in the use of the lower forms of the ".Stück," "Blue,"or" Wolf"

Jan 1, 1887

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By Walter Crafts

Structural steels containing chromium have become widely used in the last 20 years. In the earlier part of this period the major applications were in chromium-molybdenum aircraft tubing and similar special high-strength steels. During the past 10 years there has been a notable expansion in the use of chromium-bearing steel for structural purposes when welding was utilized for fabrication. The chromium-bearing steels introduced by Saklatwallal (chromium-copper), Kinzel2 (chromium-manganese-silicon), and Schultz3 (chromium-copper) are being extensively used at the present time. General Effects of Chromium Chromium is so widely known for its carbide-forming tendency that its capacity to stabilize oxygen, nitrogen, and phosphorus is often overlooked. In low-carbon steels of the structural type these so-called secondary characteristics become more prominent. For this reason also, chromium in structural steel is definitely a toughening agent. As the carbon content is increased, the more widely known hardening effect becomes more evident. In low-carbon steels chromium increases the notched-bar impact strength substantially. This property persists at subzero temperatures and is utilized for low-temperature service in chromium-copper steel.4 Chromium also reduces any tendency to strain-aging embrittlement. In addition to improving the toughness of steels with the usual impurities, chromium has the specific property of counteracting the brittleness induced by high phosphorus.5,6 In steels low in carbon and alloys, chromium has an almost negligible effect on tensile strength, and a hardening influence is noticeable only in the stronger steels. The ductility of welds adjacent to the base plate is also improved by chromium, both in the range of foolproof welding steels having strengths of less than 80,000 lb. per sq. in. as well as in the higher strength steels.

Jan 1, 1939

By Walter Crafts

Structural steels containing chromium have become widely used in the last 20 years. In the earlier part of this period the major applications were in chromium-molybdenum aircraft tubing and similar special high-strength steels. During the past 10 years there has been a notable expansion in the use of chromium-bearing steel for structural purposes when welding was utilized for fabrication. The chromium-bearing steels introduced by Saklatwallal (chromium-copper), Kinzel2 (chromium-manganese-silicon), and Schultz3 (chromium-copper) are being extensively used at the present time. General Effects of Chromium Chromium is so widely known for its carbide-forming tendency that its capacity to stabilize oxygen, nitrogen, and phosphorus is often overlooked. In low-carbon steels of the structural type these so-called secondary characteristics become more prominent. For this reason also, chromium in structural steel is definitely a toughening agent. As the carbon content is increased, the more widely known hardening effect becomes more evident. In low-carbon steels chromium increases the notched-bar impact strength substantially. This property persists at subzero temperatures and is utilized for low-temperature service in chromium-copper steel.4 Chromium also reduces any tendency to strain-aging embrittlement. In addition to improving the toughness of steels with the usual impurities, chromium has the specific property of counteracting the brittleness induced by high phosphorus.5,6 In steels low in carbon and alloys, chromium has an almost negligible effect on tensile strength, and a hardening influence is noticeable only in the stronger steels. The ductility of welds adjacent to the base plate is also improved by chromium, both in the range of foolproof welding steels having strengths of less than 80,000 lb. per sq. in. as well as in the higher strength steels.

Jan 1, 1939

By Hugh Rose

The properties of the company lie within the Pachuca district, State of Hidalgo, Mexico, connected by three railway lines with Mexico City, 55 miles southwest, and by two lines with Vera Cruz, 250 miles southeast. The ores were formerly divided by sorting into two classes, smelting and milling, the former averaging about 2 oz. gold and 335 oz. silver, the latter 0.12 oz. gold and 23 oz. silver. The smelting ores were sold to custom plants, principally the American Smelting & Refining Co. at Aguascalientes. The milling ores were treated by the patio process at the Guadalupe Hacienda, at Pachuca. This patio was probably the largest in existence at the time and continued in active operation up to March, 1910. In January, 1910, the mines and patio were sold to English interests, represented by Camp Bird Limited. Two new companies were formed, the Compania de Santa Gertrudis, S. A., to operate the mines, and the Compania Beneficiadora de Pachuca, S. A., to build and operate a custom cyanide milling plant. (Pig. 1.) Geology The historical geology of the Pachuca district is described by Fred J. Pope as follows: 1. The most recent sedimentary rooks in the district belong to the Cretaceous period. 2. The Cretaceous rocks were penetrated by large intrusions of ande-site (referred to hereafter as primary andesite) which occur as elliptical dome-shaped masses, striking northwest-southeast. These andesite bodies are from 8 to 15 miles long and from 6 to 10 miles wide. 3. A period of erosion during which the contour of the andesite domes was changed. 4. Andesite flows (secondary andesite) which rest unconformably on the primary andesites.

Jan 1, 1917

By Samuel B. Christy

" The man is always greater than his work." The training of the men who are to develop the mineral resources of the world is the most important problem connected with mining engineering. It becomes ever more important to civilization as the mineral wealth of the earth approaches exhaustion. I have therefore decided to consider a few of the more important problems arising in the training of the mining engineer, and especially those arising in America. , The Peculiar Nature of Mineral Wealth. Mining and Agriculture are the two fundamental arts. Without the latter our existence would be precarious; without the former, our civilization impossible. Agriculture furnishes that regular supply of food and raiment which leads to the growth of large communities in which cultivated leisure first becomes possible; while mining furnishes the metallic thread from which is woven that complex fabric we call civilization. But in these two arts the conditions for success are widely different. Most of the crops that the farmer reaps may be harvested year after year, and the proper fertilizers being added, he may continue the annual harvest indefinitely, while, as a result of cultivation, his farm becomes yearly more valuable. But the crop the miner reaps can be harvested but once in the history of the race. Our mineral wealth has taken unknown ages to mature in the bosom of the earth. The ripened fruit can be plucked but once. There are no fertilizers for worked-out mines. It never pays to work over a mine that has been

Jan 1, 1906

By A. B. Cox, L. W. Wark

An attempt has been made to compare the influences of the two most widely used depressants—alkalis and sodium cyanide—and the most widely used activator—copper sulfate—on the air-mineral contact induced by five sulfur-bearing compounds: (1) sodium di-ethyl dithio-phosphate (sodium Aerofloat); (2) potassium ethyl xanthate; (3) sodium di-ethyl dithiocarbamate; (4) potassium iso-amyl xanthate; (5) potassium di-n-amyl dithiocarbamate. Three different organic types are included in lhis group and for two of these types a higher and a lower homologue have been tested. The study of potassium ethyl xanthate, the preliminary results of which have been described,' was continued until there had been obtained a comprehensive account of the influence of variations in pH value and in the concentrations of xanthate, sodium cyanide and copper sulfate on the adsorption of this xanthate by galena, sphalerite, pyrite and chalcopyrite. With concentrations of copper sulfate and collector that the work with ethyl xanthate indicated would give the most illuminating. results, the other four collectors were tested, in a less exhaustive way. The same general principles determine the influence of alkalis, cyanide and copper sulfate, no matter to which type the collector belongs, but there is a gradation in the quantitative measure of such influence. In the list above, the five collectors are cited in the order of their capacity to withstand the depressants, sodium Aerofloat being the least resistant, potassium di-n-amyl dithiocarbamate the most resistant. This order coincides substantially with that of the solubilities of the heavy metal salts formed by double decomposition with the collectors, those formed from sodium Aerofloat being most soluble. There is little difference between the third and fourth members of the series, and under certain conditions their positions are reversed. In general, then, of the three types of collectors investigated, the dithiophosphate type is most easily influenced by depressants, and the

Jan 1, 1935

By D. de Fontaine

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

Jan 1, 1970

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

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

Jan 1, 1969