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By E. J. Ripling, M. W. Toaz

Tensile tests were conducted on pure magnesium and on four commercial alloys over a variety of temperatures and strain rates. The high positive slope of the ductility vs testing temperature curves that is found over a short range of testing temperatures for these materaturerials was shown to result from the fact that the microstructure was not stable at these testing temperatures. Pure magnesium did not display a transition temperature, although its sub-room temperature ductility was low. This poor ductility resulted from a grain boundary weakness. The aluminum-bearing commercial magnesium alloys had a higher ductility than the pure magnesium. ness.Thealuminum-bearingcommercialThese alloys did exhibit a transition temperature and grain boundaries that were stronger than the grain material. Both pure magnesium and the commercial alloys began initiating cracks at strains equal to one half of their fracture strain. MAGNESIUM base alloys' enormous potential as structural materials lies in their high strength to weight ratios. At present, the high strength magnesium base alloys such as AZ-80, which will be discussed later, have about as high a tensile strength to specific gravity ratio as the highest strength wrought aluminum alloy, 75s-T6, and, of course, a much higher strength to weight ratio than structural steel. Further, since the magnesium base alloys develop their high strength to weight ratios with moderate strengths and extremely light weights, the ratio of load carrying capacity to the weight of many structures is relatively higher for the magnesium base alloys than their strength to weight ratios would indicate. This results because judicious increases in section size, such as increasing the depth of bending members or adding reinforcing ribs, can frequently increase the weight of a structure linearly while the strength and stiffness increase as the second or third power of the added weight. Strength and rigidity must be designed into lightweight structures by those techniques which establish multiaxial stress states. Consequently, strong, lightweight structures frequently also possess a greater propensity toward brittle failures. In order to insure against these catastrophic failures, an extra premium must be placed on ductility and toughness in light alloys. Current knowledge of the ductility and toughness behaviors—notched behaviors—of magnesium base alloys is limited.* Most of the magnesium base alloys * The state of present knowledge regarding the effect of testing temperature on mechanical properties has recently been summar-ized by Pritchard.' crystallize in the hexagonal system, so that they are expected to exhibit a tough and ductile to brittle transition temperature. Actually, a transition temperature behavior has been reported for commercially pure magnesium in the literature, but the characteristics of this transition temperatureh uggest that it may not be a transition in the usual meaning, but simply the onset of some thermal softening, a performance much like that which face-centered-cubic lead might exhibit slightly below room temperature. If transition temperatures do exist, such important questions as the manner in which they are affected by internal variables such as chemical composition and grain size, or the effect of external variables such as rate of straining or notch severity have never been investigated. The investigation reported upon herein was undertaken in order to define some of the mechanical behaviors of the magnesium base alloys better, to gain a better understanding of the influence of some of the above listed variables, and particularly to understand their effect on ductility and toughness better. Material and Procedure Material-—Pure magnesium and four commercial alloys were used in this investigation. The alloys were selected so that chemically they made up a series with approximately the same minor alloying

Jan 1, 1957

Organization Place Date 1919 American Electrochemical Society New York, N. Y. Apr. 3-5 American Chemical Society Buffalo, N. Y. Apr. 8-11 National Foreign Trade Council : Chicago, Ill. Apr. 24-26 American Iron and Steel Institute New York, N. Y: May American Institute of Electrical Engineers Lake Placid, N. Y. June 23-27 American Society for Testing Materials..: Atlantic City, N. J. June 24-27 American Railway Bridge and Building Association Cleveland, O. Oct. 21-23

Jan 4, 1919

By R. C. Buehl, J. P. Morris

F. D. Richardson—The authors are to be congratulated on this further contribution to our knowledge of the thermodynamics of the interaction between sulphur and carbon and silicon in liquid iron. As the authors state, the influence of carbon and silicon on the activity coefficient of sulphur in liquid iron is clearly of great importance in the blast furnace, since it must cause a three to fourfold improvement in the partition of sulphur between slag and metal. The influence of increasing temperature in further increasing the activity coefficient of the sulphur in the metal in the blast furnace by increasing the carbon content is also of interest. This effect, however, is probably only part of the reason for the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing temperature. Other contributing factors are the lowering of the oxygen potential in the presence of carbon by increasing temperature and the probable increase in the activity coefficient of the lime in the slag for the same reason. The former of these effects, which works via the (CaO) + [S] = (CaS) + [O] equilibrium, might possibly account for a 70 pct improvement in the sulphur partition and the latter might give a further 50 pct improvement. C. Sherman—I would like to compliment the authors on their very careful research. If I may, I would like to show results of calculations on the carbon-sulphur-iron system similar to the ones that were shown in our paper for the silicon-sulphur-iron system. For Fe-S-C ternary system k=PHgs/PH2 x 1/(f1°) (f2°) (%S) where fs = sulphur activity coefficient fs' = fs for Fe-S system of equal pct S f3° = f2/f2 for Fe-S-C ternary system This same analysis has been used on other systems, but the results shown in fie.- 7 are for carbon and silicon. L. S. Darken—I would like to make two brief comments in addition to complimenting the authors on an apparently very precise and accurate investigation. The first is that the present work is in agreement with a calculation by Larsen and myself." Our calculation (much less precise than the present work) was based on: (1) Unpublished work on the sulphur content of molten iron (1.5 pct at 1500°C) in equilibrium with graphite and an iron sulphide slag; (2) the distribution coefficient of sulphur between slag and carbon-free liquid iron. We expressed the result in a form equivalent to log 7. = 0.18 [%C] which gives an activity coefficient (?s.) of sulphur only slightly higher than the authors find and certainly within the precision of the earlier work. My second comment concerns the correlation of the thermodynamic findings with atomistics. A rough pic- ture of the atomic arrangement in the liquid solution is rather easily conceived for this particular liquid solution containing iron, carbon, and sulphur. Carbon has a very much stronger affinity for iron than for sulphur. Hence we may conclude that a sulphur atom will but seldom be adjacent to a carbon atom—since this would be a position of high energy. From the metallic radii of iron and carbon we know that six iron atoms pack neatly around one carbon atom. Thus each carbon atom in retaining this shell of iron atoms (which latter may not be replaced by sulphur on account of the high energy requirement) decreases the available positions for each sulphur atom by six. Hence each atomic percent of carbon decreases the equilibrium sulphur content by 6 pct (of itself). Or, at low concentration each atomic percent of carbon increases the activity coefficient of sulphur by 6 pct. This is in good agreement with the observed increase (6 or 7 pct at low carbon content). It is indeed gratifying to find a case where, by such simple reasoning, quantitative agreement is found between precise data and the modern picture of the atomistics of the metallic state. J. P. Morris (authors' reply)—We would like to point out that there is an error in the equation on p. 322 of the paper. The third equation should read: ½S2 (gas) + H2 (gas) = H2S (gas) The authors wish to thank everyone for the interest they have shown in the paper. In regard to the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing the temperature, Dr. Richardson is correct in stating that the cause can be attributed only in part to the increase in activity coefficient of sulphur resulting from the rise in carbon plus silicon content of the metal with rise in temperature. However, this factor is probably an important one. The results of one experiment, performed since this report was written, indicate that at a constant temperature the addition of silicon to a melt saturated with carbon causes an increase in the activity coefficient of sulphur even though the carbon solubility is lowered. In this test, 2.5 pct silicon was added to a melt saturated with carbon and maintained at 1400°C. Although the carbon content dropped from 4.85 to 4.1 pct, the activity coefficient of sulphur was increased by about 20 pct.

Jan 1, 1951

By C. W. Spencer, Che-Yu Li, R. J. Knight

The usual reaction product for the monotectic reaction in the Bi-Se system consists of rod -shaped particles of selenium-rich liquid embedded in a single crystal matrix of At certain crystallo-graphic orientations of the matrix with respect to the reaction interface, more complex shapes are as -sumed by the liquid particles. This reaction has been examined at different growth rates and relative crystallographic orientations of the matrix with respect to the reaction interface. The uhriation in auerage particle size of the liquid phase with reaction rate has been determined at one crystallograpIzic orientation of the matrix. On a plot of logarithm of average particle diameter vs logarithm of reaction rate, data points for crystals grown at rates of 10- to 1.0 cm per hr fall near a curve of slobe -0.4. MONOTECTIC reactions in binary alloy systems are reactions of the eutectic class in which, as the system is cooled through the three-phase reaction isotherm, one liquid phase (L) decomposes to a solid phase and another liquid phase (LII).' A partial phase diagram, as taken from Hansen, showing the monotectic reaction in the Bi-Se system is given in Fig. 1. This diagram specifies the monotectic point at 618°C and 72 at. pct Se, and the monotectic reaction products as the intermetallic Bi Se3 and a liquid (LII) which contains approximately 98 at. pct Se. At a lower temperature, 217°C, this liquid may undergo a eutectic reaction in which the reaction products are BizSe3 and crystalline selenium. However, under conditions of rapid cooling, or quenching, from above 217°C, this selenium-rich liquid may be partially retained to room temperature in an amorphous or glassy state. The intermetallic BizSe3 is rhombohedral, of the space group jm;' however, for convenience it is usually represented by a hexagonal struture. A pronounced plane of cleavage, which lies perpendicular to the main axis of the rhombohedral unit cell or parallel to the basal plane of the hexagonal cell, exists in the structure. The usual monotectic reaction product consists of rod-like particles of LII embedded in a single-crystal matrix of BizSe3, although at certain crystallographic orientations of the matrix BizSe3 other more complex shapes are assumed by LII. A similar rod-like, or cylindrical, morphology for the carbide phase has been reported by westbrook7 in the a Cr-Crz3Ce eutectic structure. In this paper the morphological characteristics of the LII particles, as retained to room temperature, have been examined under conditions of varying growth rate and crystallographic orientation of the matrix BizSe3 with respect to the growth direction. EXPERIMENTAL PROCEDURE Alloy specimens corresponding to the monotectic composition, 72 at. pct, or 50 w pct Se, were prepared from 99.999 pct pure bismuth and selenium obtained from the American Smelting and Refining Co. The two elements, corresponding to a total specimen weight of approximately 30 g, were encapsulated in 13 mm OD Vycor tubing under a vacuum of 5 x X mm of Hg. The capsules were suspended on a fine platinum wire in a Bridgman-type furnace which exhibited a temperature gradient of

Jan 1, 1963

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By Tracy C. Jarrett

In 14-karat gold alloys, as in 10-karat gold alloys,3 the addition of such metals as zinc, nickel, copper and silver produces a wide range of physical and chemical properties such as color, hardness, corrosion resistance and melting points. These important factors made gold alloys desirable in the optical work and for jewelry. In 14-karat gold alloys, as well as in 10-karat or 12-karat, it is possible to have two golds of the same color, one of which will corrode more than the other, although it may be harder. Some of these alloys have been investigated by F. E. Carter,' E. M. Wise,= and L. Sterner Rainer.4 In this group of alloys the gold content of 58.3 per cent (14-karat) was held constant, while the copper varied from 36 to 24 per cent. The balance of the alloy consisted of one, two, or three of the metals silver, zinc, and nickel. All the alloys were melted in an induction furnace and cast into an ingot that measured 3 by 1/4 by 3/4 in. The method of determining the melting points, color determinations and acid test have been discussed in previous papers by the author.2, 3 It is necessary to use small test bars (Fig. I). The tensile bars were annealed at 1300oF. for 20 min. and then air-cooled. There being a very marked drop when the yield point was reached, "the drop of the beam" method was used in determining the yield point. Alloys Gold-copper.zilzc A~loys.—Gold-copper-zinc alloys melt, cast, and labricate easily. The low melting points, however, limit their use to some extent. The physical properties of these alloys are not entirely satisfactory. When the ultimate strength is satisfactory, the elongation and reduction of area are too low (Table I). Gold-copper-sinr-nickel A lloys.—In this group of alloys, in which zinc and nickel replace copper in approximately equal parts (Table I), the yield point, hardness, and ultimate strength increase with the increase of zinc and nickel content, while the reduction of area and elongation decrease. The physical properties are desirable, particularly of the white gold alloys. The alloys of this group are not difficult to cast and fabricate, and most of these colors could be used commercially. Gold-copper-nickel A lloys.—Gold-copper-nickel alloys are similar to the gold-copper-zinc and the gold-copper-zinc-nickel alloys. They do, however, possess high yield point, ultimate strength and hardness, somewhat higher than those of the other two groups mentioned (Table I). The difficulty with these alloys is that they fire-crack readily and heavy rolling is necessary between annealings. Being hard to fabricate, many

Jan 1, 1941

By Tracy C. Jarrett

In 14-karat gold alloys, as in 10-karat gold alloys,3 the addition of such metals as zinc, nickel, copper and silver produces a wide range of physical and chemical properties such as color, hardness, corrosion resistance and melting points. These important factors made gold alloys desirable in the optical work and for jewelry. In 14-karat gold alloys, as well as in 10-karat or 12-karat, it is possible to have two golds of the same color, one of which will corrode more than the other, although it may be harder. Some of these alloys have been investigated by F. E. Carter,' E. M. Wise,= and L. Sterner Rainer.4 In this group of alloys the gold content of 58.3 per cent (14-karat) was held constant, while the copper varied from 36 to 24 per cent. The balance of the alloy consisted of one, two, or three of the metals silver, zinc, and nickel. All the alloys were melted in an induction furnace and cast into an ingot that measured 3 by 1/4 by 3/4 in. The method of determining the melting points, color determinations and acid test have been discussed in previous papers by the author.2, 3 It is necessary to use small test bars (Fig. I). The tensile bars were annealed at 1300oF. for 20 min. and then air-cooled. There being a very marked drop when the yield point was reached, "the drop of the beam" method was used in determining the yield point. Alloys Gold-copper.zilzc A~loys.—Gold-copper-zinc alloys melt, cast, and labricate easily. The low melting points, however, limit their use to some extent. The physical properties of these alloys are not entirely satisfactory. When the ultimate strength is satisfactory, the elongation and reduction of area are too low (Table I). Gold-copper-sinr-nickel A lloys.—In this group of alloys, in which zinc and nickel replace copper in approximately equal parts (Table I), the yield point, hardness, and ultimate strength increase with the increase of zinc and nickel content, while the reduction of area and elongation decrease. The physical properties are desirable, particularly of the white gold alloys. The alloys of this group are not difficult to cast and fabricate, and most of these colors could be used commercially. Gold-copper-nickel A lloys.—Gold-copper-nickel alloys are similar to the gold-copper-zinc and the gold-copper-zinc-nickel alloys. They do, however, possess high yield point, ultimate strength and hardness, somewhat higher than those of the other two groups mentioned (Table I). The difficulty with these alloys is that they fire-crack readily and heavy rolling is necessary between annealings. Being hard to fabricate, many

Jan 1, 1941

By W. R. Hibbard

The term lineage was first introduced by Buergerl to denote dendritic branches, grown from a crystal nucleus during solidification from the liquid, with imper- fections in alignment of the order of 10 : to 10-4 cm. These imperfections are associated with distortions of the dendrites caused by the subsequent solidification of the inter-dendritic filling and are illustrated in Fig I. Buerger etched zinc single crystals made by the Bridgman3 method to develop this dendritic pattern and show lineage microscopically. Since maximum crystal growth in face-centered cubic metals occurs along the [IT] directions,2 lineage would appear in copper as small deviations of dendritic branches from these directions. Elam4 and others5"8 reported etching effects resulting from coring along the cube face traces of various copper alloy crystals. These traces were used by Samans8 to orient single crystals. Williamson9 noted a "lined structure (in alpha brass single crystals) consisting of an ordered arrangement of etch pits" which were probably traces of {IOO} planes but somewhat uncertain because they were never straight (that is, apparently lineage). Greningerl1 described the distortion and multiplicity of Laue spots in back reflection X ray photograms of copper single crystals showing lineage. The present investigation -includes metal-lographic, X ray, and property studies of lineage in large grain and single crystal specimens of copper. Preparation of Specimens specilnens 10 in. long 35 1/2 in. diam of oxygen-free copper (o.F.H.c.) (99.985 pet) were' melted vertically in graphite crucibles under an atmosphere of commercial nitrogen purified through a gas train including sulfuric acid, potassium chloride, magnesium chiorate, hot copper chips and phosphorus pentoxide. After a temperature of 1200°C had been maintained for 1/2 hr, the furnace was turned off and the specimens cooled at a rate of about 150°c an hour' This method of direct solidification was used by Greningerlo to produce single crystals with marked lineage and in this investigation produced a fair yield of single crystal specimens in

Jan 1, 1949

By W. R. Hibbard

The term lineage was first introduced by Buergerl to denote dendritic branches, grown from a crystal nucleus during solidification from the liquid, with imper- fections in alignment of the order of 10 : to 10-4 cm. These imperfections are associated with distortions of the dendrites caused by the subsequent solidification of the inter-dendritic filling and are illustrated in Fig I. Buerger etched zinc single crystals made by the Bridgman3 method to develop this dendritic pattern and show lineage microscopically. Since maximum crystal growth in face-centered cubic metals occurs along the [IT] directions,2 lineage would appear in copper as small deviations of dendritic branches from these directions. Elam4 and others5"8 reported etching effects resulting from coring along the cube face traces of various copper alloy crystals. These traces were used by Samans8 to orient single crystals. Williamson9 noted a "lined structure (in alpha brass single crystals) consisting of an ordered arrangement of etch pits" which were probably traces of {IOO} planes but somewhat uncertain because they were never straight (that is, apparently lineage). Greningerl1 described the distortion and multiplicity of Laue spots in back reflection X ray photograms of copper single crystals showing lineage. The present investigation -includes metal-lographic, X ray, and property studies of lineage in large grain and single crystal specimens of copper. Preparation of Specimens specilnens 10 in. long 35 1/2 in. diam of oxygen-free copper (o.F.H.c.) (99.985 pet) were' melted vertically in graphite crucibles under an atmosphere of commercial nitrogen purified through a gas train including sulfuric acid, potassium chloride, magnesium chiorate, hot copper chips and phosphorus pentoxide. After a temperature of 1200°C had been maintained for 1/2 hr, the furnace was turned off and the specimens cooled at a rate of about 150°c an hour' This method of direct solidification was used by Greningerlo to produce single crystals with marked lineage and in this investigation produced a fair yield of single crystal specimens in

Jan 1, 1949

By M. E. Wadsworth, J. R. Lewis, J. M. Quets

Samples of snythetic magnetite were reduced in hydrogen at various partial pressures and temperatures. The reaction mas found to be surface controlled and directly proportional to hydrogen partial pressure over the temperature range studied (400° to 1000°C). A transition in the mechanism occurred at approxirnately 590°C. This has been attributed to a change in the slow step of the reduction reaction resulting from the presence of stable wüstite at higher temperatures. Below 590°C the heat of activation for the reduction was found to be 14,700 cal per mole and it was 3,200 cal per mole above 590°C. THE reduction of the oxides of iron has been a subject of study and interest for many years. Edstrom1 has reviewed the work up to 1953 and his findings provide much basic information concerning details of the reduction of hematite (Fe2O3 ) and magnetite (Fe3O4) with both H2 and CO. He concluded that below 600°C the reduction of both hematite and magnetite was essentially identical, since the rate was controlled by a surface reaction at a magnetite gas interface and the iron formed was very porous. The decrease in the reduction rate for both hematite and magnetite immediately above 600°C was attributed to the formation of a stable wüstite phase across which diffusion was very slow. The wide difference in reduction kinetics for hematite and magnetite above 600°C was explained in terms of the character of the wüstite formed. The rate of magnetite reduction increased slowly with temperature beyond the minimum immediately above 600°C and rates equivalent to those observed at 550°C were not obtained until the temperature was increased beyond 850oC. Edstrom and Bitsianes2 studied the solid-state reduction of magnetite, the reaction of which can be written (4x-3)Fe + Fe3O4—4 FexO [1] where x is between 0.83 and 0.95. The rate was found to be controlled by the kinetics of transport of iron ions through the wüstite phase. Bogdandy and Riecke3 studied the kinetics of reduction of small grains of iron oxide in hydrogen and qualitatively attributed the slow step in the reduction process to the diffusion of hydrogen and water vapor through pores. McKewan4 has analysed the data of Joseph,5 Stalhane and Malmburg,6 and Lewis7 and has demonstrated that the kinetics of reduction of both hematite and magnetite are controlled by surface reactions and also that the variation in surface area during reduction must be accounted for. McKewan was able to correlate the reduction data by the equation rodo[1-(1-R)1/3] = Kt [2] where ro is the initial particle radius, do is the density of the iron oxide, R is the fraction reduced at time t, and K is a rate constant. The applicability of Eq. [2] for temperatures above 600°C where a stable wüstite phase is present, indicates the slow step in the over-all kinetics does not result from diffusion unless diffusion occurs laterally along the oxide metal interface or through a wüstite layer of constant thickness. Diffusional control through a layer of wüstite is unlikely, however, in view of the pressure effects demonstrated by Tenenbaum and Joseph,' Diepschlag,9 McKewan,10 and the results of the present study. McKewan has demonstrated a linear rate dependence on the hydrogen partial pressure over the temperature range 400" to 1050°C for the reduction of hematite.

Jan 1, 1961

By J. W. Gabelman

A study of spatial relations between uranium and other metal deposits and hydro thermally altered rocks in western Colorado demonstrated districtwide and regional zoning. The pattern was later found repeated elsewhere in the Western Hemisphere Cordillera. District mineralization centers are pipelike bodies of pervasively altered rock from which intensity-temperature-pressure gradients decreased outwardly. Uranium occurs in several zonal environments but usually is economic only in outermost zones. The general similarity of zones throughout the tectoni-cally and metallogenically uniform Cordillera may reflect a consistent hydrothermal process involving zoning. By determining positions of zones it should be possible to select for examination the most favorable small portions of districts or provinces. Mineralogical zoning has been discussed by Lindgren,l3 Graton,lo Emmons,' Blanchard,' Park and many others. It is commonly found to some extent in most mineralized areas. The existence of nonmetallic alteration envelopes around lode metal deposits and their relation to metallization were first emphasized by Lovering,l4 Burbank, Sales and Meyer," Sales,2o McKinstry,I7 Lovering and others15 and Schmitt. Also, large areas of nonmetallic alteration containing porphyry-type replacement metal disseminations have long been recognized and are described by Schwartz,25-28 Kerr and others" and Gilully. In some districts, e. g., Bingham Canyon, Utah, and Santa Rita, N.M., base metal lode deposits and their alteration envelopes are zoned around large altered areas which contain porphyry copper replacement disseminations; however, the spatial and genetic relations between lodes and replacement disseminations and their associated alterations do not seem to have received sufficient attention. Bodies of altered rock containing porphyry-type replacement disseminations are many times larger than the alteration envelopes containing lode deposits. The two types are rarely superimposed. They occur adjacent to or independent of one another, but they are believed to be related through the mechanism of zoning as suggested by Gabelman and Boyer. 5'6 Most of the significant lode metal deposits are distributed around central pipelike bodies of strong, pervasive, nonmetallic alteration which may or may

Jan 1, 1962

By R. D. Nelson, F. E. Bowman

Assumptions are made of ideal mixing and that the density of silver can be obtained by extrapolating reported liquid density-temperature data through the freezing point back to the temperature range of interest. The results of this procedure using liquid silver density data of Kirshenbaum et al.5 are presented in Table I1 where it is observed that agreement is everywhere within <0.1 pct and generally is within 0.05 pct. Because the Sn-Ag alloys are dilute, the assumption of ideal behavior is, therefore, probably justified. In conclusion, the densities of dilute liquid solutions of silver in tin have been determined. Even for concentrations as low as 0.1 pct, the effect of silver on the density of liquid tin is clearly measurable. This work also suggests that for dilute alloys at temperatures far below the freezing point of the solute metal, densities may be accurately calculated by extrapolation of the pure metal data without having recourse to physical measurement on the alloy itself. plutonium having a grain size of about 100 µ. This paper presents data showing that large elongations of fine-grained a Pu can be obtained by using slow deformation rates. Large plasticity, however, of a Pu in compression has been observed.4 Reductions in thickness of 90 pct have been observed with no edge cracking. These large reductions are accompanied by concurrent re-crystallization. The deformation modes, which are quite complex, have been studied extensively by observing the deformation microstructures of polished surfaces that had been deformed in compression.5-7 Although slip apparently is a predominant mode of deformation at room temperature, grain boundary sliding and concurrent recrystallization become more predominant at high a temperatures.4&apos;7 Although recovery occurs,8,9 no grain growth has been reported in a Pu even at temperatures near the a =ß equilibrium temperature (-115oC), which is 0.7 of the calculated melting temperature of a Pu.10 From studies on other materials, it appears that high elongations can be obtained in alloys when the THE purpose of this technical note is to present briefly some data revealing high ductility of a Pu, which is normally considered brittle. The very low ductility of a Pu in tension has been reported by many investigators.&apos;-3 Gardner,1 for example, reported that the total elongation of a Pu at a testing speed of 0.015 ipm is less than 0.1 pct at room temperature and only about 1 pct at 100°C. The only tensile creep studies that have been reported&apos; indicate no large ductility, but they were performed on relatively low purity

Jan 1, 1970

By Charles Colcock Jones

In the winter of 1902, while occupying the position of mining and examining engineer for the Mountain Copper Co., Ltd., of Keswick, Cal., I had .occasion to discuss with the General Manager, among other things, the question of the enormous waste of sulphur in smelting cupriferous pyrite ore, and to cast about for means to utilize this waste or to render the fumes innocuous to vegetation. The decreasing rate of production of California farms, the consequent need of fertilizers, and the opportunity thus offered to utilize large quantities of sulphuric acid in the manufacture of superphosphates naturally brought the subject to the practical and commercial side of phosphates. I was informed that the company had made efforts to find phosphates in the West, without success. I advised as a start placing inquiries for phosphate deposits on the Pacific coast in the current mining journals. This was done, with the result that in January, 1903, from an advertisement in the Mining and Scientific Press we got track of a deposit in Rich county, Utah, through T. J. Wilson, of the Southern Pacific railroad in San Francisco. As soon as snow in the mountains would permit, in May, 1903, I undertook an examination of the property, with the result of recognizing the importance of the find, in spite of its lack of facilities for transportation at a commercial figure. On June 15, 1903, I concluded my report by saying, "This may be one of the world&apos;s deposits of phosphates." On Nov. 17, 1903, I concluded my report for the season in the following words : " I have now no hesitation in saying that I believe the Carboniferous formation so largely developed in the Wasatch mountains of Utah and the mountains of the Great Basin will prove to be one of the greatest storehouses of phosphoric acid in the world." Early History. In the summer of 1897 R. A. Pidcock, a mail carrier of Ogden, Utah, while on a prospecting trip camped on " 12 mile," a branch of

Jan 1, 1914

By W. C. Maurer

A study of the mechanics of shear failure of rock under pressure has been made. The transition from brittle to ductile failure occurs when the friction along the fracture surfaces exceeds the shear strength of the rock. A machine has been developed for measuring both the shear strength of rock and the friction along rock fracture surfaces. In this shear machine, the fractures are forced along definite planes; as a result, the rock is stronger than in compression tests where the fractures choose the weakest paths through the specimens. Friction is composed of several forces: (1) the forces to slide irregulurities on surfaces over each other; (2) forces to shear some of these irregularities; (3) molecular attractions across the fractures; and (4) forces required to break bonds resulting from melting and welding at the tips of irregularities on the surfaces. Friction along rock fracture surfaces is not proportional to contact pressure as usually assumed; instead, it increases as the contact pressure raised to the 0.4 to 0.8 power. INTRODUCTION It is difficult to produce tensile stresses under the high compressive stresses present in the earth; therefore, in deep drilling and geological faulting, shear failure predominates. This shear failure mechanism is complicated because rock is a heterogeneous material containing pore spaces, microfractures, elastic discontinuities and other imperfections. A study of shear failure of rock under pressure has been made to obtain a better understanding of this complex mechanism. A machine has been developed and used to measure the shear strength of rock and friction along sheared surfaces. This machine has certain advantages over the compression test — shear properties can be measured under low normal stresses and shear stress and normal stress can be varied independently. The first part of this paper is a description of shear failure of rock under pressure. The role of shear strength and friction along fracture surfaces in the shear failure mechanism will be discussed. The second part consists of a description of the shear machine and a discussion of the shear strength and friction data obtained using this machine. It will be shown that shear strength depends upon the size of the stressed zone, and that friction does not increase linearly with contact pressure as usually assumed. Attempts are made to relate some of the new concepts to tectonic failure and to dril ling. SHEAR FAILURE IN ROCK TRIAXIAL TESTS The shear failure mechanism is illustrated by the triaxial test shown in Fig. 1. In this test, a cylindrical rock specimen is subjected to a confining pressure, PC, and an axial pressure, pa. These external pressures produce normal a and shear T stresses on inclined planes within the specimen equal to1 where 0 is the angle between the specimen axis and a normal to the inclined plane. Fig. 2 shows how triaxial specimens deform as the axial pressure is increased. The pressure is

Jan 1, 1966

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By H. Conrad

The strain hardening associated with the creep of magnesium single crystals at room temperatu.Je was investigated by shear tests in which the direction of stressing was reversed a number of times after creep in a <100> direction. The strain hardening was strongly anisotropic; the largest amount occurring in the direction of flow and the least 180 deg to this. The time law for creep changed from a parabolic type to logarithmic for the first and subsequent reversals of stress. For a given stress the creep strain decreased significantly for the first and second reversals and then only slightly for subsequent reversals. The logarithmic creep constant a changed in a similar manner. A linear relationship was observed between the creep strain for a given reversal and the stress. The slope for the third reversal yielded a strain hardening coefficient 12 to 16 times greater than that observed for unidirectional flow. Al-though no recovery was observed upon resting at room temperature, the hardening resulting from stress reversals could be completely removed by heating to 450" C. PREVIOUS work1.&apos; indicated that the creep rate of magnesium single crystals tested in the temperature range of 78" to 364°K decreased with time. This was attributed to an increase in internal stress resulting from an accumulation of dislocations at internal obstacles. The object of the present investigation was to further evaluate the nature of this hardening by conducting tests in which the direction of stressing is changed after previous creep in shear in a given slip direction. Previous to 1950 three investigations indicated that a Bauschinger effect3 occurred for single crystals as well as polycrystals brass in tension compression,

Jan 1, 1960

By R. Simon

The sources of energy dissipation for concentrated loadings on rock are considered in an attempt to account for the experimentally measured magnitude of the work required to break out a unit volume of rock from the free surface of an essentially semi-infinite medium. It is concluded that most of this work probably represents the elastic strain energy developed by the loading in a much larger volume of rock beneath the loaded region than the volume of the rock fragment broken out to the side of the loaded region. This strain energy is largely dissipated in the form of stress waves generated by the high rate of unloading produced by the propagating cracks. The energies associated with the formation of the new surfaces of the cracks and with the stress waves generated directly by the loading process are computed to be negligibly small. Possibilities for improving the utilization of energy to drill rod. subject to the geometrical limitations imposed by down-hole operation, are discussed. It is pointed out that any such possible improvements would probably have to be differential ones, since each rock configuration of more favorabIe loading geometry that can be created down the hole is accompanied by a complementary configuration of less favorable loading geometry. INTRODUCTION Dislodging each cubic inch of rock from the bottom of the hole by the action of a bit requires the expenditure of an amount of energy that varies from approximately 5,000 in.-lb to approximately 100,000 in.-lb, depending on the hardness of the rock, or, more technically, upon its fragmentation strength.1 In this paper we will discuss (I) why the energy expended in drilling is so large, (2) what happens to this energy upon completion of the drilling process, and (3) what are the possibilities for reducing the magnitude of the energy required to drill rock. DETERMINATION OF ROCK DRILLING ENERGY The volume of rock removed per unit time from the bottom of a hole of diameter D is evidently (7/4)D2R, where R is the rate of penetration of the bit. If P is the rate at which work is done by the bit on the rock at the bottom of the hole, the energy required to break out a unit volume of rock is given by: Ev =(4/p) P/D2R............(i) For rotary drilling, of either the rolling-cone or drag-bit varicty, P = 2pLN, where L is the torque resistance to rotation at the bottom of the hole and N is the rate of rotation of the bit. L is essentially the same as the torque measured at the rotary table only when drilling in shallow holes. The energies expended in rotating the drill string against the frictional resistance of the walls of the hole and and against the viscous drag of the drilling fluid are extraneous to the subject under consideration, although these may be much greater in magnitude than E, when drilling in a deep hole. For percussion drilling, P = fE where f is the percussion frequency and E is the work done on the rock per impact. The latter quantity can be both computed and measured for a percussion drilling machine. 2 (Under satisfactory drilling conditions, defined in terms of ranges of numerical values of certain dimensionless parameters, E is only 30 to 50 per cent less than the impact energy of the striker.2) Alternatively, E, may be measured directly by dropping chisels shaped like bit edges, backed by rigid weights, onto the surfaces of laboratory rock samples of effectively semi-infinite extent. Under these circumstances, essentially all of the impact energy is converted to work done on the rock, and the relationships among volume of rock broken out, chisel shape, impact energy and indexing distances can be obtained.3 The values of the energy required to break out a unit volume of rock under favorable circumstances are substantially in agreement for rotary drilling, percussion drilling and drop testing at atmospheric pressure. The energy per unit volume is a quantity of the order of magnitude of roughly twice the com-pressive strength of the rock as measured by a uniaxial loading test. The phrase "order of magnitude" in this paper means from about 1/3 as much to 3 times as much; i.e., the energy per unit volume may range from roughly the same up to several times

By R. W. Smith

Many industries such as the cement industry handle large quantities of limestone and clay slurries. However, at present very little is known about the flow properties, such as friction loss due to flow of slurries in pipelines. This lack of knowledge has made it often very difficult to calculate the total dynamic head of a proposed slurry handling system, and therefore has often made the selection of correct size slurry handling equipment difficult. Because of lack of knowledge about slurry flow a study of slurry flow theory has been made at the Portland Cement Association&apos;s Research and Development Laboratory with the idea of developing a method whereby friction losses due to slurry flow may be predicted for any size pipeline. The flow equations developed have been checked by pilot plant size equipment. DERIVATION OF FLOW EQUATIONS It has been known for some time that limestone and clay slurries handled in cement plants do not flow in the same manner as a Newtonian fluid such as water. When a Newtonian fluid flows the shear stress at any flow velocity is proportional to the rate of shear. This phenomenon can be illustrated by a line (Figure 1). The viscosity of the fluid is the slope of the curve. Thus, the flow properties of the material may be characterized by a single materials constant: viscosity. When a non-Newtonian fluid with the type of characteristics exhibited by limestone and clay slurr-ries flow, a similar curve can be constructed (Figure 2). This graph is a shear diagram of a Bingham plastic non-Newtonian fluid. It should be noted that with the Bingham(1) plastic type of flow viscosity, the slope of the curve, is still an important materials constant. In addition, however, there is another materials constant, namely the yield stress of the material. One way to visualize this constant is to consider it as the amount of energy that must be put into a Bingham plastic material to start it flowing.

Jan 1, 1961

By C. E. Tsoutrelis

A new method for determining rock drillability in diamond drilling is discussed; the method takes into consideration both penetration rate and bit wear. The method is based on drilling a rock specimen under controlled laboratory conditions using a model bit. The technique used for determining the experimental variables is extremely simple, quick, and reliable. Drillability is then determined by the mathematics of drilling. In considering the different factors that affect diamond drilling performance, the nature of the rock to be drilled is of outmost importance since it affects significantly the drilling costs and such other variables as bit type and design, drilling thrust, and bit rotary speed. Many attempts have been made to study this effect by correlating actual drilling performances either to certain physical properties of the rock being drilled1-? or to test drilling data obtained under laboratory conditions.7-13 These attempts were aimed at providing a reliable method of predicting by simple means the expected rock behavior in actual drilling, thus giving the engineer a tool to use in estimating drilling performances and costs in different types of rock. The purpose of this paper is to describe such a method by which rock drillability (a term used in the technical literature to describe rock behavior in drilling) could be determined in diamond drilling. It is believed that the proposed simple and reliable method will cover the need of the mining industry for a workable method of measuring the drillability of rocks. It should be emphasized, however, that since drill-ability depends on the physical properties of rock and each drilling process (diamond, percussive, rotary) is affected by different or partly different rock properties,14-l6 the proposed method of determining rock drillability cannot be extended to the other drilling processes. The results presented in this paper form part of an extensive three-year research program carried out by the author in the laboratories of the Greek Institute of Geology and Subsurface Research. During this period the effects of the physical properties of rocks and of such operational variables as drilling thrust and bit rotary speed in diamond drilling were investigated in detail. DRILLABILITY CONCEPT The literature is not devoid of drillability studies. While there are a number of investigators1,3,5-7,9-0,12-13,17 who have attempted to establish by direct methods (i.e., drilling tests under laboratory conditions) or indirect (i.e., through a physical property of rock) an index from which the drilling performance in a given rock may be estimated, very few6-7,9,12, of the proposed methods seem to be of much practical value to the diamond drilling engineer and none to date has been universally accepted. Commenting on the proposed methods for assessing rock drillability, Fish14 remarks that "for a measure of drillability to be accepted it is essential that penetration rate at a given thrust and bit life are elucidated as otherwise the method is of little value." This statement should be examined in more detail by making use of the penetration rate-drilling time diagram obtained in drilling a rock under constant operational conditions. Furthermore, the merits of using this diagram to describe rock drillability will be pointed out. At the same time reference will be made to this diagram when discussing some previously proposed methods. Fig. 1 illustrates such a diagram for three rocks,A, B, and C, which have been diamond drilled under identical conditions. It is assumed here that rocks A and B have the same initial penetration rate, i.e., VOA = Vog, but since rock B is more abrasive than A, rapid bit wear occurs and as a result the fall of its penetration rate with respect to time is more vigorous than in rock A. This is shown graphically by a steeper V = f(t) (0 curve in this rock than in rock A. Rock C has a lower initial penetration rate, due to higher strength properties16 but since it is not very abrasive, only a slight fall of its penetration rate occurs during drilling (in this category are some limestone and marbles with compressive strength above 1000 kg per sq cm). It follows from the foregoing considerations that the characteristic for each rock curve (I) is a function of (i), the penetration rate of the rock Vo recorded at the instant of commencing drilling, which determines the starting point of the curve (1) on the y-axis and (ii), the abrasive rock properties which determine the rate of fall of Vo with respect to time. Thus, curve (I) provides an actual picture of the rock behavior in drilling for given operational conditions, and it can be used with complete satisfaction to assess rock drillability. It can be seen clearly from Fig. I that proposed methods for assessing rock drillability by measuring the

Jan 1, 1970

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.&apos; The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8&apos;10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968