Search Documents

By C. R. Dodson, D. Goodwill, E. H. Mayer

The paper summarizes the historical background of the pressure-volume-temperature analyses of reservoir fluids, the errors involved in both the sampling and testing of reservoir fluids, the type of information required of a PVT determination, and the field conditions that limit the application of any one analysis. Particular emphasis is placed on the necessity for approximating as closely as possible the liberation sequence occurring in the producing formation, flow string, and surface separators. A combined differential and flash or "composite" liberation is suggested as the best means of approximating this liberation sequence. HISTORICAL BACKGROUND Petroleum reservoir engineering commonly is considered to be one of the newest fields of petroleum science, yet much work of a theoretical and intuitive nature was done many years before the modern techniques of reservoir analyses were developed. The period 1910-1924 saw considerable work in the field of reservoir behavior done by the U. S. Bureau of Mines. This work:.' although entirely theoretical, pointed out the importance of gas in the recovery of oil from the reservoir. The statement by J. 0. Lewis that 20 per cent or less of the oil originally in place in a pool was recovered from the ground under uncurtailed production conditions caused some operators to re-examine and modify their production methods. However, though these works showed methods of production that have subsequently resulted in greater oil recoveries, they in general went unnoticed, even though there was a fear that the nation's petroleum resources were being exhausted. The period 1924-1933 saw the industry take considerably more interest in reservoir behavior because of an unfounded fear of its inability to replace oil reserves, the possibility of government regulation, and the energy of one man, Henry L. Doherty. Doherty aroused heated discussions in the industry concerning conservation. To prove or disprove his theories the first experimental work on the reservoir behavior of petroleum was undertaken. The papers of Dow and Calkin,' Beecher and Parkhurst," and Mills and Heitheckere are classics although their experimental procedures were crude. These papers proved that the properties of petroleum in the reservoir are quite dissimilar to the properties measured at the well head. Gas dissolved in the oil phase was recognized as having considerable importance as had been predicted by the earlier theorists. Slightly later Miller and his co-workers assembled the first text correlating all the known data on the reservoir behavior of petroleum and used, these data to show the economic value of conservation. Quantitative application of pressure-volume-temperature analyses of reservoir fluids was given in the paper of Coleman, Wilde, and Moore"; this work showed that with sufficient laboratory and production data prediction of reservoir behavior was possible. The refined sampling and labora-

Jan 1, 1953

By J. W. Hickman, E. A Gulbransen

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By J. B. Hess, C. S. Barrett

Single crystal rods of cadmium collapse under uniaxial compression into peculiar kinks if the (0001) glide plane is nearly parallel to the axis of compression. In his report first describing this behavior, Orowan1 proposed that these "kink bands" do not develop entirely by ordinary gliding and twinning but by a special mechanism in which glide lamellae of uniform thickness snap abruptly to a tilted position that permits lattice continuity across the glide planes. He concluded that a portion of each boundary of a kink band consists of a plane (non-crystallo-graphic) which bisects the angle between the glide planes on the two sides of it, and along which the bending and the dislocations are concentrated. The data presented by Orowan seemed to us to be insuffcient to conclude that a wholly new mechanism of deformation was responsible for the kinks. Therefore, we have investigated zinc, which is hexagonal close-packed and has an axial ratio near to cadmium, to see whether similar bands are produced, and whether the ordinary mechanisms of glide, bend-gliding, twinning, and the formation of deformation bands can account for its mode of deformation. We find that kinks form profusely in zinc as shown in Fig 1. The structure of these kinks, reported below, seems to require no new mechanism for their explanation, but indicates that kink bands are a special form of deformation bands and develop gradually, solely from basal glide. A theory covering the formation and structure of the bands is presented in detail because it is seldom possible to study deformation bands under such simple conditions, yet many principles applying to these kinks should also apply to deformation bands in general. Experimental Procedures Single crystal rods of 2-3 mm diam and 10-15 cm length were grown by the Brideman technique from swaged wire of Horsehead Special zinc in un-coated pyrex tubes. Orientations of the rods were determined with an optical goniometer after cleaving the rods at liquid air temperature. Crystals of desired orientations were then selected and used as "seeds" to grow additional crystals approximately 4 ft in length from which all specimens were cut. The wires were compressed in two ways: in a simple hydraulic handpress —a "soft" machine—and in a Riehle hydraulic testing machine modified to produce very "stiff" action by the simple expedient of inserting lengths of steel bars at the sides of the zinc crystals between the compression plates. For metallographic examination, the specimens were mounted in sealing wax. Hand polishing was employed, with no grits coarser than No. 1 paper; following the abrasives about 0.025 in. was removed by an etch-polishing reagent.* Final etching to reveal ori-

Jan 1, 1950

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

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By H. L. Gilbert, C. Travis Anderson, W. J. Kroll

IN a previous paper,1 the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.2 When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8in. in diameter. The supply of direct current of high amperage for producing the . desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flexible tubing of the movable electrode, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decided to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 1900°C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica according to the reaction: Si02 + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1948

By H. L. Gilbert, C. T. Anderson, W. J. Kroll

In a previous paper,' the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.% When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8 in. in diameter. The supply of direct current of high amperage for producing the desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flcxible tubing of the movable electrodc, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decsed to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 19oo"C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica accortling to the reaction: SiO² + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1949

By L. J. Dijkstra

During the past several years an extensive study has been made of the internal friction of iron containing carbon or nitrogen in solid solution.1,2,3,4,5 It has been found that a sharp peak is observed in a plot of the internal friction vs. temperature of measurement. With a frequency of about one cycle per second, this peak occurs at 20°C for N and 36°C for C. The physical origin of this anomalous internal friction was traced by Snoekl to the local tetragonal symmetry of the interstitial positions in body centered cubic (bcc) iron. A change in stress induces a change in the equilibrium distribution of the interstitial atoms among the three types of interstitial positions, the three types corresponding to the three directions along which the tetragonal axis may lie. It is the continual striving of the interstitial atoms to maintain an equilibrium distribution that gives rise to a phase lag between strain and stress during oscillation, and hence, to internal friction. A similar type of internal friction has been observed in the bcc lattice of tantalum containing in interstitial solid solution C, N or 06. The theory of this anomalous internal friction leads to the prediction that its magnitude is strictly proportional to the concentration of either the carbon or the nitrogen in solid solution, provided the concentrations are small. This prediction has been verified3 for the range of solubilities ohtainable in alpha iron. This proportionality provides us with a new tool for the study of nitrogen and carbon in alpha iron. It thus enables one directly to follow the precipitation of either of these solute atoms from solid solution and also directly to measure their solubility as a function of temperature. A preliminary study of precipitation using this method has already been presented by the author.3 The purpose of this paper is to present more extensive observations upon the precipitation of N and C in alpha iron, as well as to present observations upon the solubility of N and C in alpha iron which, at least in the lower tempera- ture range, are believed more accurate than those previously obtained by other methods. The interpretation of the observations upon precipitation involves the use of the appropriate equilibrium diagrams. For ease of future reference in this paper the equilibriunl diagrams for the Fe-N and Fe-C systems are accordingly reproduced as Fig 1 and 2, respective]y. Experimental Procedure The specimens were made of West-inghouse Puron iron and consisted of wires 0.025 in. in diam and about 1 ft long. By a wet hydrogen treatment the specimens were purified of C and N. In

Jan 1, 1950

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By R. H. Tien

This paper presents an analytical solution of the problem of freezing of a semi-infinite slab with constant surface temperature; in this analysis accoz~nt is taken of the heat evolution during the solid-state transformations in the frozen skin. The regions where transformations occur are treated as plane isothermal heat sources; i.e., the rates of transformations are assumed to be infinite. In the model considered, three plane heat sources are assumed to be present in the frozen solid. The solution yields the temperature distribution in the solid, the rates of movement of the heat sources , and the rate of movement of the solidification front. It is shown that, although the sum of the heats of transformations in the solid is about 20 or 43 pct of the heat of fusion of iron or manganese, respectively, the effect of the heat evolution in solid-state transformations on the rate of solidification is insignzficant. IN several recent mathematical studies of solidification of liquid metals'-3 no account was taken of the heat evolution accompanying the solid-state transformations. In the case of, for example, steel, there are several phase transformations 6 -y, y -a, and the magnetic transformation. Whether or not a significant error is introduced into the mathematical simulation of solidification processes by the omission of the heat effects associated with these phase transformations is not known. The purpose of the present study is to investigate the effect of these phase transformations on the temperature distribution and the rate of solidification based solely on the heat transfer point of view. That is, for the sake of simplicity, freezing of a pure metal with solid-state transformations will be considered. The mathematical model which represents the present problem includes four moving heat sources representing freezing and phase transformations, 6— y — a — ferromagnetic. The thermal properties such as conductivity and specific heat, and so forth, are different from one phase to the other. But they are considered to be uniform over any particular phase. The usual Fourier heat flow law is employed. The concept of conservation of energy is applied at every heat source in order to estimate their rate of movement. The temperature distribution in the solid and the positions where transformations occur are expressed analytically in terms of error function solutions and four coefficients which are determined from four nonlinear algebraic equations. These coefficients can be calculated either by trial and error or by any numerical method. MATHEMATICAL ANALYSIS Fig. 1 is a schematic diagram showing the zones of different phases 1, 2, 3, and 4 in the solidified portion of a semi-infinite pure liquid metal. The heat is subtracted from the system at x = 0 which is maintained

Jan 1, 1968

Copper ores from small mines in the area south of Tucson, where the Twin Buttes mine is located, were first operated in the 1880's. Today this area is one of the great copper mining centers of the world. In 1963, Anaconda Company acquired the property from Banner Mining Company and in recent years joined with AMAX in a 50/50 partnership to work the Twin Buttes property. From the beginning, Anaconda had relied on conveyors to remove overburden, oxide material for eventual leaching, and ore from the open pit. In the large st preproduction stripping program in mining history, Anaconda in a four-year period (1965 to 1969) removed 266 million tons of overburden of an average depth of 500 ft (152 m) lying over the ore body. The alluvium overburden was stripped by scrapers carrying 70 to 80 tons and push-loaded by two D9 tractors operating in tandem. The scrapers delivered their loads to bins which fed a 60 in. (1.52 m) conveyor having a capacity of 8500 tph. The 25% slope belt conveyor, which was 2100 ft (640 m) long, transported the material to the brow of the pit, where it was transferred to an 8300 ft (2530 m) surface belt to a 1000 ton loadout bin. At this point, the overburden was trucked to the sites of the tailings ponds, where it was used for dam construction. During 1976, the one billionth ton of overburden was removed from the Twin Buttes mine. The Twin Buttes quartz monzonite porphyry contains only scattered mineralization of which chalcopyrite is the most abundant mineral, associated with chalcocite, covellite, minor bornite, and several oxide minerals. Oxidation has progressed to variable depths of up to several hundred feet below the base of the alluvium. Because of the depth of the sulfide and oxide ores and hard rock waste, two in-pit crushers and conveyor systems were also installed for their transport out of the pit; and in 1976 a third crusher and conveyor system was installed lower in the pit for waste rock only. The two initial crushing and conveying systems were designed to handle any of three functions: crushing waste to be disposed of by a rail-mounted stacker -conveyor, crushing oxide ore for conveyor and then truck transport to stockpiles for future leaching, and primary crushing of sulfide ore for conveyor transport to the two 30 in. by 70 in. (0.76 by 1.78 m) secondary crushers and the two 7 ft (2. 13 m) standards and four 7 ft shortheads in the third and fourth stage crushing plant. A third standard crusher has been in- stalled recently. Mining is done by 15 yd (11.5 cum) shovels which load 100- and 150-ton

Jan 1, 1978

By Walter Crafts, C. M. Offenhauer

In a previous study of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is 2 more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about I to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, I per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to I-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudo-martensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously1 that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By A. W. Schlechten, W. J. Kroll

As this paper is written, the only method for the commercial production of lithium metal is by the fusion electrolysis of LiCl-KCl mixtures, as first proposed by Guntz.2 The details of the industrial process have not been made public but Osborg8 stated that an efficiency of more than go pct is obtained with a lithium metal recovery above 95 pct and that the metal is 99.5 pct pure. Pletenev9 gave a power consumption of 66 kw-hr per kilogram of lithium metal produced with a salt consumption of 9 kg of LiCl and 0.4 kg of KCI. Pletenev's figures indicate a somewhat lower recovery than that given by Osborg. In a recent report on German lithium plants, Motock7 gives figures that are also less favorable than those reported by Osborg. At the German plants the lithium recovery in electrolysis was only 83.4 pct, with a power consumption of too kw-hr per kilogram of lithium. The metal averaged only 97 pct pure, with sodium and potassium as the chief impurities. The presence of SO2, SO3, Si02, Ba, Ca, and appreciable amounts of Na and Fe2O3 were especially disturbing in the electrolysis, and it was necessary to run the cell for some time to eliminate most of these impurities and condition the bath. It may be noted here that most of these impurities do not interfere with a thermal reduction process. These facts show that the present method of producing lithium is fairly efficient and would suggest that other methods could not compete. However, fusion electrolysis has certain drawbacks, such as the necessity of supplying costly, low-voltage direct current and of collecting and processing the anodic chlorine if it is not to be wasted. An even greater disadvantage is that lithium chloride must be used for an electrolyte. It is one of the most expensive salts of lithium, since it cannot be produced in anhydrous form by precipitation from aqueous solution, as is done with LiF or Li2CO3. The reduction of lithium by a vacuum process similar to the ferrosilicon method for the production of magnesium would have certain advantages. Small units, such as Pidgeon retorts, would give flexibility of production to meet demand, and a small plant would require moderate capital outlay. There is a possibility of using idle Government-owned magnesium plants for such purposes. The raw materials needed for vacuum thermal reduction would not have to be extremely pure, especially with respect to the iron and calcium content. This paper describes a series of experiments to determine the effectiveness of various agents for the reduction of lithium compounds. The investigation is part of a program of vacuum metallurgy con-

Jan 1, 1947

Duval Corporation, the copper -producing subsidiary of Pennzoil United, Incorporated, operates two plants south of Tucson, Arizona: Esperanza and Sierrita. The newest, the Sierrita mine and mill, came into full production in 1971 at a rate of 72,000 tpd (now 87,000 tpd) which at that time made it the largest designed copper plant in the world. In 1968, the largest milling units then available were selected; these included fourteen 16$ ft by 19 ft long ball mills (5 m by 5. 9 m), each equipped with a 3,000 hp motor. The primary crushing plant contains two 60 in. by 89 in. Allis- Chalmers gyratories; each is constructed for two-side dumping by 120- and 150-ton trucks. Access to the maintenance areas to service the drive motors, eccentrics, apron feeders, and speedup conveyor is through hatches between the crushers. This area also contains a good- sized elevator and a stairway. The rather shallow dump pocket, the 300 -ton crushed ore pocket, and the overall design make for a fine, compact arrangement for two 60 in. crushers installed in a total height of 89 ft (27. 13 m) from dump level to top-of-concrete at the lowest level beneath the collecting or speedup belt. This efficient layout is reflected in the short changeout time for mantle and concaves (8 and 30 hours respectively) and the low crushing cost of $0.0416 per ton (first half of 1975). The crushers are installed on 64 ft (19.5 m) centers (Bougainville and Palabora, both with 54 in. crushers, are 55 and 43 ft or 16.76 and 13. 1 m respectively). The switchgear room is located between the truck dumping positions on one side of the installation and the hydroset units on the other side, with dust collecting equipment mounted over the latter. Protection of these units from rocks falling from the trucks is provided by concrete walls. Truck dumping is controlled from a central 25 ft high (7.6 m) control room, which permits fine observation of operations. Removal of oversize boulders from the dump pockets is done with a hydraulic grapple or a rock hook or sling attached to the auxiliary crane hook. Spare mantle stands and a maintenance room with a zinc melting furnace are located at one end of the surface facilities. The maintenance room is equipped with an access door for the crane, which is equipped with 80- and 20-ton hoists. The two 84 in. (2. 135 m) apron feeders receiving the 6 in. (152 mm) crushed rock discharge onto a 72 in. (1. 83 m) collecting and wear belt operated at a speed compatible with the 60 in. (1.524 m) takeaway belt running at a speed of 630 fpm (192 mpm). This belt feeds a 54 in.

Jan 1, 1978

By Walter Crafts, C. M. Offenhauer

In a previous study of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is 2 more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about I to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, I per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to I-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudo-martensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously1 that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By R. T. DeHoff

A new approach to the measurement of the size distribution of particulate structures imbedded in opaque bodies is developed. The method is based upon the assumption of a general two-parameter distribution curve, and the estimation of these two parameters from three well-known counting measurements made upon metallogvaphic sections. The total number of particles in the system is also a product of the analysis. Application of the method with the assumption of the logarithmiconorma1 disfribution function is developed in detail. A complete description of the geometry of a particulate structure requires the determination of the size distribution of particles. The problem of estimating the size distribution of particles of a particular phase in a multiphase system, or the grain-size distribution in a homogeneous system, has been approached by many investigators.'-'0 All of the solutions proposed by these investigators share the following characteristics. a) A minimum of several hundred particle sections in the microstructure must be examined, and some characteristic dimension recorded, such as area,3'5 intercept length,6"9 or diameter.1'2'4'10 b) The resulting data must undergo a series of fairly complex calculations to generate the empirical histogram which describes the size distribution in three dimensions. c) In order to manipulate the result, the histogram must be fitted to some assumed mathematical formula, using the attendant statistical procedures. d) With two notable exceptions,8,10 the particles must be spherical. The measurements and calculations involved are in general very tedious and time-consuming, with the logical result that much effort has been expended in the development of equipment which will perform these tasks automatically and semiautomati-cally.9,11-15 considerable success has been achieved in this area, but the equipment is in general expensive, and usually places stringent requirements On the quality of microstructure which can be reliably analyzed. In laboratories which do not possess such equip- ment, the analysis of geometry is usually limited to measuring total properties of the microstructures, such as volume fraction and interfacial area, because the measurements required are much simpler to make. The determination of size distributions rarely is undertaken. The development which is presented in this paper permits the estimation of size distributions of three-dimensional structures from the same simple counting measurements which are required to determine the surface area and volume fraction of the particulate structure, and one other counting measurement. The basic approach that is used is to assume a general mathematical form for the distribution, which is described by two parameters (as the normal distribution is described by assigning values to the mean and the standard deviation), and then estimate these two parameters from the results of the counting measurements. The introduction of a third counting measurement also permits the evaluation of the number of particles per unit volume, Nv.

Jan 1, 1965

By C. Burton Clark, J. Spotts McDowell

Refractories are defined as "materials having the ability to retain their physical shapes and chemical identities when subjected to high temperatures," or as "nonmetallic materials suitable for the construction or lining of furnaces operated at high temperatures." While resistance to "high" temperatures is thus the primary requirement for refractory materials, it is by no means the sole requirement. They must be able to withstand thermal shock resulting from rapid heating or cooling; other stresses induced by temperature change; pressures from the weights of furnace parts or contents; mechanical wear (abrasion) resulting from movement of furnace contents; and chemical attack by heated solids, liquids, or gases. Refractories of many kinds are needed for the many and widely diversified industrial applications. Those in greatest demand are classified on the basis of composition or properties into a few main groups, known as alumina-silica, silica, basic and insulating refractories. In each of these groups there are several classes. In addition to those included in the main groups, there are various special refractories, including silicon carbide, carbon, zircon, zirconia, alumina, and several others. Alumina-silica refractories comprise two main divisions: fire clay and high-alumina. The alumina content of fire-clay refractories covers the range from about 45 pct to 18 pct, and the silica content from 50 pct to 80 pct. The alumina content of fired high-alumina refractories ranges from about 99 pct to 45 pct, and the silica content from about 0.5 pct to 50 pct. Silica refractories of the different classes contain 94 pct to 97 pct silica. Basic refractories include periclase (magnesite), chrome spinel, forsterite, and dolomite. Refractory materials, including insulating firebrick, are supplied mainly as preformed shapes. Other products include bonding mortars and high temperature cements, ramming mixtures, plastic firebrick, hydraulic setting castables, dead-burned grain magnesite, and dead-burned dolomite. Refractory brick are classified on the basis of their physical form as Standard Sizes and Special Shapes. The Standard Sizes are brick of certain definite sizes and relatively simple design which are used in sufficient amounts to permit quantity production. The brick most widely used are the standard 9 in. X 4 ½ in. X 2 ½in. and 9 in. X 4½in. X 3 in. straights and corresponding series of sizes. All brick of nonstandard dimensions are regarded as "special shapes." They include a wide variety of brick regularly used for specific services, such as baffle tile for boilers, checker brick for regenerators, and others; together with shapes of special design manufactured on particular orders from designs submitted by the user. Not included in the broad classifications of Standard Sizes and Special Shapes are several specific-service refractory products, usually made by companies which specialize in their manufacture, or in some cases by the consumers themselves. These products include

Jan 1, 1960

By Harmon D. Nine

DISCONTINUITIES in the strain vs cycles to failure (S-N) fatigue curves have been reported for polycrystalline materials by Porter and Levy for copper,&apos; by Benham and Ford for mild steel,&apos; and by Williams and Stevens for 18/5 stainless steel.3 However, the considerable scatter of the points for polycrystalline materials have made a statistical analysis of the data necessary to confirm the discontinuities. By using oriented single crystals of high-purity material and low grown-in dislocation content, the reproducibility has been improved to a degree which makes statistical analysis unnecessary and clearly shows discontinuities in the S-N curves. A recent publication4 reports an abrupt change of slope in the S-N curve for ( 100) axially oriented copper single crystals fatigued in torsion. The reported discontinuities in the S-N curve, along with a different mode of failure in the two branches of the curve, have been interpreted as being due to two different amplitude-dependent mechanisms. Further work on copper single crystals of (111) axial orientation has now been completed which supports the existence of an amplitude-dependent change in the mechanism of fatigue. In the present study torsional-fatigue experiments were performed at room temperature in air on (111) axially oriented single crystals. The crystals were grown and prepared as reported in Ref. 4. Two different methods of growing the crystals also discussed in Ref. 4 produced crystals of two different perfections: Type I with dislocation density of >l06 per sq cm and Type I1 with dislocation density of <l05 per sq cm. In accordance with the accepted hypothesis that crystal flaws are primarily responsible for the scatter of fatigue lifetimes, particularly at low amplitudes, the values for the three lowest amplitudes for Type I crystal are believed to be uncertain. They are marked in braces in Fig. 1. On the other hand, at amplitudes above a surface shear strain (SSS) of *0.003, the data for both types of crystals are in agreement. Most remarkably the S-N curve for torsional fatigue of (111)-oriented single crystals is composed of three segments separated by rather large discontinuities, Fig. 1. Metallographic and X-ray measurements indicate that the lower branch corresponds to the low-amplitude (F) region of the (100) copper single-crystal results as discussed in Ref. 4, and the two upper branches correspond to the high-amplitude (H) region. The lower discontinuity in the (111) S-N curve and metallographic evidence give further support to the hypothesis that different mechanisms of failure operate for high and low strain amplitudes. Reference to the resolved shear stress diagram, Fig. 2, shows that the highest stressed systems in

Jan 1, 1965

By R. J. Borg, C. E. Birchenall

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

By J. J. Calaman, D. H. Fleming

DURING 1950 the jet-piercing process was used commercially in the piercing of primary blast-holes in magnetic taconite at the preliminary taconite plant of .the Erie Mining Co., Aurora, Minn. The Erie Mining Co. purchased a jet-piercing machine and associated equipment in 1949, and the machine has been in operation since its installation in the summer of that year. An overall view of the pit with the JPM-1 jet-piercing machine in operation is shown in Fig. 1. During three months of 1949 and continuously since February 1950, production piercing took place under all pit conditions. By the end of October 1950, a total of 15,000 linear ft of hole had been pierced in an open pit handling an average of 1200 to 1800 tons of crude a day in one 8-hr shift. While it is recognized that this output does not approach the millions of tons a year planned for the developing Minnesota taconite projects, the machine as a unit has been operating under conditions probably more adverse than those that eventually will be encountered in the large operations. This pilot operation has permitted evaluation of the piercing problem in the full-scale taconite plant. This paper describes jet-piercing process funda- mentals, important features of the latest jet-piercing burners and machine, actual piercing results obtained, and new developments that give promise of materially increasing overall process efficiency. To produce the blasthole, jet-piercing utilizes thermal energy, as contrasted with the application of mechanical energy in churn drills and jackham-mers. The heart of the process may be termed a tailored flame produced by a rocket-type burner, thermodynamically similar in every respect to that of the giant rockets being developed for military purposes. The heat release in the combustion chamber of the burner is about 50x10&apos; Btu per cu ft per hr as compared with 5x10&apos; for most modern steam generators.* Combustion of liquid petroleum fuels (kerosine, diesel oil, or No. 2 fuel oil) with gaseous oxygen in the burner chamber at pressures of 100 to 200 psi results in temperatures of about 4300°F. Expansion of the hot combustion gases through divergent nozzles produces high-temperature supersonic jets having measured velocities of about 6000 fps. Impinging the flame jets on rock causes a thin surface layer to expand and break away from the base as a result of the thermally induced stresses. This spalling action is aided further in chert and quartzite by the 0.82 pct volume change resulting from the 6 to p quartz inversion at 1066"F.t The dynamic action of the jets whisks the spalled rock

Jan 1, 1952