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By J. E. Hanafee, G. J. London

MANY studies of the deformation behavior of materials under a superimposed hydrostatic pressure have shown that materials brittle at ambient pressure behave in a ductile manner under pressure. Thus, with a metal such as beryllium which possesses relatively low ductility, but otherwise exhibits quite useful physical and mechanical properties, hydrostatic pressure may be particularly useful for both forming beryllium shapes and studying its deformation behavior. In fact, it has been found1"4 that polycrystal-line beryllium in both ingot and powder form appears to behave in a more ductile manner on a macroscopic level in a hydrostatic pressure environment, and it has been suggested2 that this is due to activating a new slip mode. Furthermore, Andrews and Radcliffe5 have found pressure induced nonbasal dislocation activity in hot pressed beryllium. Recently6 it has been shown in "c-axis" compression tests under hydro-static pressures up to 28 kbars that the shear stress needed to cause slip with a Burgers vector out of the basal plane (pyramidal slip) does not change with increasing pressure in beryllium with a purity of some 99.5 pct. This material is equivalent or more pure than the beryllium used in the previous pressure studies. Thus, it appears, as suggested by Inoue et al.,3 that the hydrostatic pressure affects the fracture stress rather than the stress necessary to activate pyramidal slip in beryllium. However, in "c-axis" pressure tests on high purity 12 zone pass beryllium (˜50 ppm total impurities) the macroscopic compression stress needed to cause pyramidal slip was considerably lower than that at ambient pressure.6 It has further been shown that alloying beryllium with nickel and copper in the range 2-5 wt pct also favors the occurrence of pyramidal slip in "c-axis" compression tests,7'8 while lower amounts of nickel and copper do not have significant effects. In the present study the combined effect of hydrostatic pressure and alloying high purity beryllium on the shear stress needed to cause pyramidal slip has been ascertained. A 2.5 wt pct Cu alloy was selected as the first alloy to study as this level of copper did favor pyramidal slip at room pressure. A high purity (12 zone pass) single crystal of beryllium 0.3 by 0.1 by 0.1 in. was cut and polished by an orientation and lapping technique8 so that the top and bottom compression surfaces were parallel and within 3 min of arc to the (0001) plane and the sides parallel to the {l010} and {ll20} planes. In these compression specimens, therefore, the resolved shear stress was nearly zero on both the basal and prism planes, and slip was restricted to pyramidal systems. Analysis of slip traces on the two lateral surfaces served to accurately identify the active slip planes.6'9 The pressure unit was a modified piston-cylinder device fitted with a manganin transducer coil arrangement which continuously monitored and recorded the hydro-static pressure. The load on the specimen was measured by a strain gage load cell which operated entirely within the pressure chamber. This load cell was calibrated before and after each pressure cycle at room pressure in situ and the calibration did not vary more than ±1 pet. These techniques and devices have been previously described in more detail.6 Successively higher compressive stresses were applied to the single crystal under a superimposed hydrostatic pressure until fracture occurred. The strain rate was (4.5 ± 2.0) x 10-6 sec-1 and the average rate of pressure application and release was approximately 0.3 kbars per min. As the load on the specimen was applied by the piston which was used to increase the hydrostatic pressure, the pressure increased during the compression test. This increase ranged from 0.0 to 0.8 kbars, and the maximum hydrostatic pressures are quoted in Fig. 1. The lateral surfaces of the specimen were examined in a light microscope after each pressurization/stress cycle so that the stress at the onset of {1122} pyramidal slip could be ascertained. Post compression height measurements allowed the plastic strain in the specimen to be evaluated to within 0.03 pct. The resulting compression stress-plastic strain curve is shown in Fig. 1 with results of a "c-axis" test on a similar Be-2.5 wt pct Cu single

Jan 1, 1970

By J. Washburn, R. Drouard, E. R. Parker

Temperature dependence of the rate of recovery in zinc single crystals after a simple shear deformation at low temperature was investigated. Some tentative suggestions regarding the annealed and strain-hardened states of a crystal are discussed. RECOVERY may be defined as the gradual return of the mechanical and physical properties of strain-hardened metal to those characteristic of the annealed material; an increase in temperature increases the rate of recovery. The annealing process in strain-hardened polycrystalline metals is complicated by the inhomogeneity of strain which always exists in aggregates. Polygonization in bent regions of the crystals and growth of new almost strain-free grains starting at points of severe local distortion1-:' make it almost impossible to isolate and study the recovery process. Homogeneously strained single crystals, however, do not polygonize or re-crystallize and hence they can be used advantageously to study recovery. In such crystals strain hardening is completely removed by recovery alone. Since recovery is a process whereby certain lattice disturbances introduced by plastic flow are gradually reduced, a knowledge of the rate and temperature dependence of this process for various conditions of prestrain might be helpful in formulating a model of the strain-hardened state. For simplicity it seemed desirable to limit the type of prestrain to the simplest obtainable, i.e., simple shear strain. In the experiments to be described, recovery was studied by observing changes in the stress-strain curve of prestrained zinc single crystals held for various times at temperatures above that employed for straining. Single crystals were grown from the melt by a modified Bridgeman technique from Horse Head Special zinc 99.99 pct pure, and from spectrographically pure zinc 99.999 pct pure. They were grown as 1 in. diameter spheres and acid-machined' to the final specimen contour. The test section was a cylinder about 1/8 in. high and 3/4 in. in diameter. The conical sections adjacent to the test section were cemented into the grips so the load could be transmitted to the crystal as uniformly as possible. The specimens were oriented so that in testing the maximum shear stress was applied along one of the slip directions, [2110], in the (0001) plane. Details of the production and testing of such specimens have been presented.' Each test was carried out according to the following schedule: 1—The crystal was strained at — 50°C until it reached a maximum shear stress, ,,,. The strain rate was approximately 5 pct per min in all cases. 2—After straining, the crystal was unloaded before the temperature was changed. Unloading required about 3 min. 3—The temperature of the specimen was then increased from — 50°C to the temperature, T, of recovery. This change in temperature was completed in a time of less than 2 min. The specimen remained at temperature, T, for a time, t, which differed for the various specimens. 4—Thereafter the temperature was again reduced to — 50 °C in approximately 3 min. 5—While at —50°C, the stress-strain curve after recovery was obtained. 6—The specimen was then unloaded and annealed for 1 hr at 375 °C in a helium atmosphere to bring about complete recovery. Cooling to room temperature after anneal required 90 min. 7—The same crystal could be re-used for another test because the plastic properties after annealing closely duplicated those of the original crystal. The specimen was immersed during the test in a bath of methyl alcohol which, through a system of tubes, could be pumped through either of two heat exchangers to regulate the temperature; this was accomplished by circulating the liquid through coils immersed in a bath of acetone and dry ice for cooling or in a bath of warm water for heating. Test temperatures were thus maintained constant within ±1°C. The — 50°C temperature was low enough so that no measurable recovery occurred during unloading and reloading. The stress-strain curve continued after recovery along a path below, but approximately parallel to, the path of a curve obtained in an uninterrupted test. Fig. 1 shows some of the results from a specimen of 99.999 pct Zn. The amount of downward displacement of the curve due to recovery was a

Jan 1, 1954

By T. Yamasaki, S. Usu

Adsorption of potassium dodecyl xanthate from aqueous solutions on artificial and natural zinc sul-fides was studied by means of infrared absorption spectroscopy. The adsorption species and their stabilities varied depending upon the conditions of the surfaces of the zinc sulfides. Adsorption products were analyzed after they had been removed from the surface with pyridine. Zinc dodecyl xanthate was confirmed for surfaces covered with oxidized products while dodecyl alcohol and carbon disulfide were detected on purified or weakly oxidized surfaces. It is of great significance to study the adsorbed species of collectors on the surface of sulfide minerals with a view of increasing our understanding of the mechanism of flotation. Compared with other methods, infrared spectroscopy promises to be of particular value in determining the nature of the species adsorbed at the mineral/solution interface since it gives direct identification of the adsorption products; and, furthermore, it has an advantage over the electron diffraction technique which has been employed in similar problems in that infrared spectroscopy utilizes radiation of very low energy so that the probability of changing the unstable surface films during examination should be correspondingly decreased. Infrared spectroscopic studies concerned with sulfide mineral flotation have already been reported by several investigators on zinc sulfide-hexanthi01' and lead sulfide-xanthate2,3 systems. The purpose of the present study was to investigate the adsorption of potassium dodecyl xanthate (KDX) at the zinc sulfide-aqueous solution interface by means of infrared spectroscopy. Rarely is the pure zinc sulfide-xanthate system encountered in practical flotation since zinc sulfide is usually activated with small amounts of certain metallic ions, such as copper ion. However, investigation of the pure zinc sulfide-xanthate system appeared promising for studying the fundamental mechanism of the adsorption of xanthate on the sulfide minerals. Although there are few cases where xanthates having an alkyl radical higher than hexyl are employed in practical operations, KDX was used in this study since it was reported that the adsorbability of xanthate on zinc sulfide was increased with an increasing number of carbon atoms of the alkyl radicals.4 EXPERIMENTAL Samples: Experiments were made on artificial zinc sulfide and natural sphalerite. The artificial zinc sulfide was obtained commercially from Dainihon Toryo Co. as a fluorescent pigment of the purest grade A. Considering the fact that there are often cases where the surface of sulfide minerals are apt to be oxidized so that the adsorption of xanthate at sulfide mineral/solution interfaces may be substantially affected, two different procedures were employed in preparing the samples of the artificial zinc sulfide. 1) The zinc sulfide was washed with hot concentrated ammonium chloride solution (300 g per liter) to remove surface oxidation products and followed by washing with deoxygenated hot distilled water by centrifugation until the constant electric conductivity of the solution was reached (Sample I) (specific conductivity of the solution = 8.6 x l0-5 ohm-' cm-'). 2) Sample I in a suspension of 5% by weight was oxidized with a 1.5% aqueous hydrogen peroxide solution for about one hour, and then was washed with distilled water as mentioned in the preparation of Sample I (Sample 11) (specific conductivity of the solution = 1.0 x 10"4 ohm-' cm-'). Both Samples I and II were dried under vacuum and stored in a vacuum desiccator. The specific surface areas of the samples determined by the BET method using carbon dioxide gas were 19 x l04 cm2 per g for Sample I and 35 x l04 cm2 per g for Sample 11. In addition, a sample which was derived from Sample I was also prepared. In 40 ml of 3 x 10-2 M zinc sulfate solution was placed 2 g of Sample I for 2 hours, washed with distilled water by successive centrifugation until no sulfate ion could be detected and dried under vacuum (Sample 111). The purpose of this treatment will be described later. Natural sphalerite was carefully selected by hand, ground in a mechanical agate mortar for about 40

Jan 1, 1965

By D. P. Kedzie, R. A. Dodd

The fatigue strength, fatigue hardening, and effect of fatigue deformation on subsequent age hardening of supersaturated Al(Cu) solid solutions have been determined as functions of alloy composition and temperature. The fatigue strength/tensile strength ratios, determined at 150°, 25°, and -195°C, decreased with increase in alloy content for all temperatures, but the F.S./U.T.S. ratios at -195°C decreased much more rapidly than did the ratios for 150" and 25°C. This suggested that strain aging and/or age hardening occurred during tests at higher temperatures. Additionally, the F.S./U.T.S. ratios at 150°C exceeded those at 25°C for all compositions, indicating greater strengthening during fatigue at 150°C. The effect of fatigue or tensile deformation at 150°, 25°, and -195°C on subsequent age hardening showed that the deformatzon increased the rate of precipitation and indicated that mechanically produced vacancies were probably formed during deformation. Fatigue hardening was studied at 150°, 25°, and -195°C, and the effect of room-temperature rests after 10 and 100 cycles was examined. The results confirmed that strain aging occurred at the higher temperatures . DURING the last 15 years various mechanisms of fatigue crack nucleation and growth based on dislocation and vacancy interactions, operating singly or collectively, have been proposed. The probable consensus of present opinion is that the fatigue process in pure metals essentially involves dislocation interactions, and that vacancies formed by such interactions play a minor or inconsequential role. However, there is some evidence that age-hardened alloys tend to overage during fatigue, probably by local vacancy-enhanced diffusion, and strain aging also might be important in selected cases. Furthermore, it has been established that the behavior of quenched-in vacancies in Al(Cu) and other solid solutions is composition-sensitive. Therefore, it seemed worthwhile to investigate various aspects of the fatigue behavior of supersaturated Al(Cu) alloys and to examine the results in terms of vacancy-enhanced effects. EXPERIMENTAL The alloys used in this investigation were prepared from 99.994 wt pet A1 and OFHC copper, the latter containing 0.04 pet 0 as the principal impurity. Six alloys were made, containing, by actual analysis, 0.58, 0.96, 1.96, 2.85, 4.45, and 5.51 wt pet Cu. They were induction-melted in air in graphite crucibles, cast as 7-in. by 7/8-in.-diam rods in graphite molds, and hot-rolled to 5/8 in. diam. The experimental work was a three-part program involving the determination of a) 10' cycle fatigue stresses as a function of alloy composition and temperature; b) the effect of fatigue deformation on subsequent aging of the supersaturated alloys; and c) fatigue hardening as a function of alloy composition and temperature. For determining the 105 cycle fatigue stresses, a portion of the 5/8-in. stock was machined into Krouse rotating cantilever beam fatigue specimens, 2 in. in length by 1/4 in. minimum diameter. These were tested at +150°, 25°, and -195°C (liquid nitrogen) on a Krouse high-speed machine, with special weights to provide lower -than-normal loading ranges, this being necessitated by the small load requirements of those alloys of lower copper content. For the high-temperature tests a small resistance heater was designed to clear the collets and fit in between the chucks, while for the low-temperature tests a hollow nylon cylinder was used, having closed ends drilled to pass a fatigue specimen, and positioned similarly to the heater. A plexiglass container completely enclosed the fatigue machine; rubber gloves fixed to ports in the walls enabled the machine to be operated from outside the box. A tray of magnesium perchlorate dried the air in the container and prevented both atmospheric corrosion fatigue at room and elevated temperatures and troublesome ice build-up at low temperatures. A total of ten to fifteen specimens was used for each combination of alloy composition and temperature. The result of each test was plotted on a standard S-N diagram, and the next stress was selected on the basis of the trends indicated by previous specimens. In this manner a small portion of the S-N diagram was constructed, and the 105 cycle fatigue stress obtained. Small Krouse fatigue specimens were also used to study the effect of cyclic prestrain on subsequent

Jan 1, 1964

By Roswell P. Angier, Herbert S. Kalish, Henry H. Hausner

POWDER metallurgical methods as applied to zirconium are of great interest because they permit not only the fabrication of parts directly to shape with a minimum loss of material but also the utilization of scrap, and the metal may be processed at temperatures well below the melting point. There are two difficulties involved in the melting of zirconium: 1—High vacuum is necessary for melting, and 2—zirconium reduces nearly all oxides so that it is difficult to find a suitable crucible material. The purest material, zirconium crystal bar, is expensive, and the methods of subsequent fabrication are limited. Cold rolling or extrusion of zirconium crystal bar is suitable for making certain shaped parts, but where melting is involved, the purity of the metal is invariably decreased, and a method of casting to a definite shape does not seem to be feasible. Where it is necessary to hot roll, zirconium must be covered with a steel or copper jacket to protect it from the air. This is necessarily a costly operation. Where annealing of zirconium is necessary it must be conducted in a high vacuum. In an investigation of powder metallurgical methods for zirconium, the zirconium powder used should be characterized by the following properties: 1— Highest degree of purity, 2—uniformity in particle shape and particle size distribution, 3—low compression ratio, and 4—satisfactory strength of the compacted powder (green strength). Zirconium powders have been made by two methods: By the reduction of zirconium tetrachloride (ZrC1,) with sodium,2' *•B "nd by the reduction of zirconium oxide with calcium and calcium chloride." The first method represents one of the earliest attempts to make pure zirconium metal, and the sintered product from this powder is extremely brittle. The second method of making zirconium powder is far more successful, but the powder made in this way has an extremely low apparent density and, therefore, a high compression ratio which makes it difficult to use it for powder metallurgical purposes. For these reasons the above-mentioned zirconium powders were not used in this investigation. To obtain sintered zirconium compacts of highest 'purity and good ductility, it was first necessary to produce a suitable powder. Pure zirconium has been made chiefly by two methods. The iodide method, from which the product is "crystal bar" zirconium, was developed first.'." By this purification process very soft, pure, and ductile zirconium metal can be produced. The second method, developed by the U. S. Bureau of Mines, is the reduction of zirconium chloride with magnesium." The sponge zirconium thus produced is also soft, pure, and ductile.

Jan 1, 1952

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. S. Busk

TWO groups of binary alloys were prepared. The first group consisted of those elements relatively soluble in magnesium: Li, Al, Zn, Ga, Ag, Cd, In, Sn, Hg, T1, Pb, and Bi. These are predominately Group B elements. The second group consisted of most of the remaining metallic elements, all of which are relatively insoluble in magnesium: As, Au, Ba, Ca, Ce, Cu, Ir, La, Mn, Ni, Pd, Pt, Rh, Sb, Si, Te, Ti, W, and Zr. These are all Group A, transition, or rare earth elements. Alloys of the first group were prepared by melting sublimed magnesium and elements as pure as obtainable in a graphite crucible, using a standard flux1 for protection. The melts were poured into a small graphite mold to produce 3xY4 in. diam slugs. Spectroscopic analyses were made of each slug. In all cases, the total impurity content was less than 0.05 pct. The slugs were then heat treated 5°C below the eutectic temperature until complete solution, as judged metallographically, was obtained. Filings from the center of the slugs were compacted at room temperature into 1/2 in. long x 1/4 in. diam cylinders, sealed in pyrex under 1/2 atm of purified argon, annealed at the heat-treating temperature for 1 hr, and quenched in water. After the X-ray diffraction patterns were made, each compact was analyzed chemically for the solute. It was found that the Mg-Li alloys reacted during filing to reduce the Li in solid solution. For this series of alloys, the slug was cold worked, annealed in purified argon, the surface dissolved in dilute HC1 to a depth of about 0.005 in., and the X-ray exposure made on the fresh surface. This procedure resulted in sharp, continuous lines and in true values for the lattice parameters. The alloys in the second group were prepared in the same way except that about 1 wt pct of each solute was added. Since the solubility limit was exceeded, not all the solute dissolved. These alloys were analyzed spectroscopically only to confirm the presence of the solute. The diffraction patterns were of the back-reflec-tion type using the characteristic copper radiation* and a flat cassette. Both the film and the specimen were rotated. The specimen temperature was maintained at 25" ± 1°C. The films had sharp lines; their diameters were measured directly to 0.01 cm. The parameters were calculated from the line diameters using a modified version of Cohen's extrapolation method.2 his method effectively eliminates systematic errors such as film shrinkage, inaccurate alignment, and non-precise film-to-speci-men distance. The random errors were minimized

Jan 1, 1951

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 subcritical 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.1 Westgren, Phragmén and Negresco2 identified the following carbides in chromium steels: [Cementite Fe3C (containing up to about 15 per cent Cr) Trigonal carbide Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide Cr4C (or Cr23C3) (containing 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 studies, sections of the diagram were established. This diagram showed the presence of the special carbide Cr7Ca 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 r per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7Ca occurs in chromium steels containing more than about 1 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 1-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 auenchine. The quenched bars were cut into

Jan 1, 1942

By G. W. Binkley, G. K. Dumbauld, F. A. Brooks, B. E. Morgan

In recent years, oil well cementing compositions have been developed with low densities, controlled set strengths, and satisfactory thickening times. With the introduction of the permanent-type well completion method for cementing wells, another property—that of rate of filtration or water loss to permeable formations— has become important. Laboratory data show that cement slurries prepared with oil, water, bentonite, and calcium lignosulfonate possess satisfactory thickening times, strengths, and filtration properties for primary cementing of casing and for squeeze cementing with the permanent-type well completion technique. Cementing compositions have been prepared with oil-in-water emulsions varying in composition from 60 cc water and 20 cc oil per 100 gm cement to 90 cc water and 45 cc oil per 100 gm cement. These compositions have contained from 0.4 to 5.0 per cent calcium lignosulfonate by weight of dry cement. Slurries prepared from these compositions weigh 11.4 to 13.1 lb/ga1 and have filtration rates of from 10 cc to approximately 100 cc in 30-min API tests at room temperature. The unfiltered emulsion cements develop one-day tensile strengths of 60 to 220 psi; and the filtered mass sets to tensile strengths of 60 to 150 psi in 12 hours and develops strengths of 320 to 515 psi in seven days when cured at 125° F. Field experience gained from 13 field mixing jobs demonstrates the utility of the emulsion cement for permanent-type squeeze cementing operations. INTRODUCTION In recent years, research in oil well cementing composition has been directed toward the development of cements having low densities, controlled set strengths, satisfactory thickening times, and low rates of water loss by filtration. Two well cementing compositions that have been developed with these properties are the modified cements containing, respectively, 12 and 25 per cent bentonite clay and various concentrations of calcium lignosulfonate1,2 In a search for other ways to incorporate these characteristics in a cementing composition, consideration was given to the rheological properties of oil-emulsion drilling fluids. Many of the desirable properties observed in oil-emulsion drilling fluids are equally advantageous in a cementing composition. For example, low water loss by filtration and low density, which are inherent characteristics of these oil-in-water emulsions, are desirable for many oil well cementing operations. Furthermore, oil-emulsion slurries have lubricating properties similar to those of oil-emulsion muds, a factor which should provide ease of rotation of casing during primary cementing operations. The properties of lubrication and low filtration may be of special value in both primary and squeeze cementing operations encountered in slim-hole drilling. Studies in the preparation of oil emulsion systems have pointed out the need for violent agitation in order to disperse the oil into the water phase. It was thought, therefore,

Jan 1, 1957

By P. D. Hunt, I. Johnson, M. G. Chasanov, H. M. Feder

The solubilities of the transition metals from scundium to nickel, inclusive, in liquid cadmium were determined by sampling saturated solutions. At 400°C these solubilities (ppm) are:Sc, Co, 22; Ni, 12000. Relative partial molal enthalpies and excess partial molal entropies at infinite dilution for the solutes Cr, Mn, Fe, and Co are compared zoitlz similar data for the post-transition metals. Three new intermetallic phases, ScCd,, TiCd, and Ti,Cd, encozaztered in the course of this work, are reported. Measurements of the solubility of the 3-d transition metals in liquid cadmium have been reported' only for iron. The present measurements for the entire series were made as an aid to the study of the systematics of alloy formation. EXPERIMENTAL The apparatus and sampling techniques used for the solubility determinations were similar to those described by Martin etal.' Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple sheathed in recrystallized alumina and immersed in the solution. The thermocouple was recalibrated periodically during the course of the investigation. Thermocouple voltages were measured to the neares 0.01 mv with a Rubicon model 2732 potentiometer. A scaled-down version of the apparratus, in which the total metal charge was about 90 g, was employed to measure the solubility of scandium. Two-mm ID Vycor filter pipets were used to sample the scandium-cadmiurn solutions; the samples weighed about 2g- Cadmium with a minimum purity of 99.95 pct was used; the only impurities detected spectrochem-ically were C'u and Mg, both less than 10 ppm. The purities of the other metals were: scandium, 99.9 pct; titanium. 99.92 pct; vanadium, 99.9 pct; chromium, 99).99 pct; manganese, 99.9+ pct; iron, 99.90 pct; cobalt, 99.95 pct; and nickel, 99.96 pct. Solidified melts were routinely analyzed spectro-graphically. No significant contamination by the crucible, sampling pipets, or other materials of construction was observed. The entire specimen obtained by sampling was dissolved to preclude analytical errors due to segregation on cooling. Colorimetric methods3 were used for the analyses of cobalt (2-nitroso-l-naphthol), manganese (permanganate), nickel (dimethylglyoxime), titanium (peroxide), and vanadium (thiocyanate).4 Chromium, iron, and scandium were neutron-irradiated to produce The dissolved samples were gamma-counted to determine solute concentration.For the separation of intermediate phases from cadmium-rich alloys selective leaching by saturated ammonium nitrate solutions was employed. The concentration of cadmium in the successive leaches was followed polarographically and the process was terminated when the rate of cadmium dissolution decreased markedly. For the further investigation of intermediate phases 1/4- in. diam powder compacts were pressed at 80,000 psi and annealed in argon at 315" to 330°C for 10 days. Larger quantities of alloys were prepared in sealed tantalum capsules heated in a rocking furnace.

Jan 1, 1962

By R. A. Kinzie

THE major operating costs in a cement plant are labor, power, and fuel. The opportunities and methods of savings in labor and power parallel other industries. Because our industry's use of fuel is large and its method of use is unique, the devices adapted for saving fuel are of interest. In normal practice the raw material in the form of a dry powder or a mud is fed to a rotating inclined cylinder where it is dried, calcined, and clinkered. In a Lepol kiln the raw material is rolled up into little balls with water in the nodulizer, fed to a traveling grate on which it is dried and partially calcined and tben to a short kiln where the process is finished. The more usual methods of saving heat have been the use of long kilns with chains in wet process plants and the use of waste heat boilers in dry plants (fig. 1). At the Santa Cruz plant we have used a Lepol system kiln and achieved a fuel 'economy of 4.7 gal per bbl of clinker or about 704,-000 Btu per bbl. This can be compared with our old kilns using the same fuel and raw material which consume 7.8 gal per bbl or 1,130,000 Btu per bbl. These are gross Btu and not the net figures usually used in reports of foreign companies. Our average consumption for 1948 was 708,000 Btu per bbl of Lepol clinker, based on cement sold, and oil purchased. The overall fuel consumption for 1948 was 6.61 gal per bbl. The Lepol system consists of a nodulizer, a grate, and a kiln. There is the usual accessory equipment which is similar to that used in other cement plants. The following description covers the equipment in operation at our plant. The nodulizer is a cylinder 8 ft 10 in. in diam by 18 ft long set on a slope of 1/2 in. per ft, and rotated at about 10 rpm. It is driven by a 50 hp wound rotor motor drawing about 9 kw. The inside of the shell is cleaned by a continuously operating scraper which draws 0.1 kw. The dry raw material is fed to the nodulizer where, being sprayed with water, it rolls into small spheres about 90 pct being between 1/2 and 1 in. in diam and containing about 15 pct water. The nodules fall on the traveling grate where the hot gas from the kiln is pulled down through the

Jan 1, 1951

By R. A. Kinzie

THE major operating costs in a cement plant are labor, power, and fuel. The opportunities and methods of savings in labor and power parallel other industries. Because our industry's use of fuel is large and its method of use is unique, the devices adapted for saving fuel are of interest. In normal practice the raw material in the form of a dry powder or a mud is fed to a rotating inclined cylinder where it is dried, calcined, and clinkered. In a Lepol kiln the raw material is rolled up into little balls with water in the nodulizer, fed to a traveling grate on which it is dried and partially calcined and tben to a short kiln where the process is finished. The more usual methods of saving heat have been the use of long kilns with chains in wet process plants and the use of waste heat boilers in dry plants (fig. 1). At the Santa Cruz plant we have used a Lepol system kiln and achieved a fuel 'economy of 4.7 gal per bbl of clinker or about 704,-000 Btu per bbl. This can be compared with our old kilns using the same fuel and raw material which consume 7.8 gal per bbl or 1,130,000 Btu per bbl. These are gross Btu and not the net figures usually used in reports of foreign companies. Our average consumption for 1948 was 708,000 Btu per bbl of Lepol clinker, based on cement sold, and oil purchased. The overall fuel consumption for 1948 was 6.61 gal per bbl. The Lepol system consists of a nodulizer, a grate, and a kiln. There is the usual accessory equipment which is similar to that used in other cement plants. The following description covers the equipment in operation at our plant. The nodulizer is a cylinder 8 ft 10 in. in diam by 18 ft long set on a slope of 1/2 in. per ft, and rotated at about 10 rpm. It is driven by a 50 hp wound rotor motor drawing about 9 kw. The inside of the shell is cleaned by a continuously operating scraper which draws 0.1 kw. The dry raw material is fed to the nodulizer where, being sprayed with water, it rolls into small spheres about 90 pct being between 1/2 and 1 in. in diam and containing about 15 pct water. The nodules fall on the traveling grate where the hot gas from the kiln is pulled down through the

Jan 1, 1951

By G. W. P. Rengstorff

In an effort to find an oxidation-resistant alloy of molybdenum, binary and ternary alloys containing aluminum, chromium, cobalt, iron, nickel, silicon, titanium, tungsten, vanadium, and zirconium were screened. Fourteen other alloying additions were also tested. Many of the alloys were more oxidation-resistant than molybdenum, but none were entirely satisfactory. MOLYBDENUM oxidizes extremely rapidly above 1450°F in air. At 1800°F, a loss of metal at the rate of 0.1 in. in 4 hr is typical. The high speed of this oxidation may be judged by comparison with the oxidation rate of 0.1 in. per year (0.00005 in. in 4 hr), sometimes taken as the maximum permissible oxidation rate at 1800°F for a satisfactory Fe-Cr-Ni alloy. Great strides have been made in the development of coatings and cladding to protect molybdenum from oxidizing atmospheres. These developments in surface protection will undoubtedly make it possible to take advantage of the excellent hot strength of molybdellum and its alloys in many new applications. Still, even the best coating can protect molybdenum only as long as the surface layer is unbroken. Research was undertaken to determine whether an alloy of molybdenum could be found which would resist oxidation. Such an alloy would not deteriorate suddenly when the protective surface layer was destroyed in a small area. In seeking an alloy of molybdenum to resist oxidation, the physical properties of molybdenum could not be sacrificed entirely. The development of an alloy with the desired resistance to oxidation was not achieved. The information obtained on the effect of a large number of elements on the oxidation of molybdenum is, however, of value in the development of coatings. Indeed, many of the alloys tested for oxidation resistance were already known to have poor mechanical properties but were tested to aid in the development of coatings. Oxidation of Molybdenum The rapid oxidation of molybdenum is usually attributed to the volatility of Moo,,. Gulbransen and Wysong have shown that molybdenum oxidizes very slowly up to 850°F, the temperature at which the oxide film begins to evaporate. Melting as well as evaporation of molybdenum oxides promotes the oxidation of molybdenum. MoO melts at 1465°F. MOO, the oxide which is believed to form at the metal-oxide interface, combines with MoO, to form a eutectic having a melting point of 1432°F.' The liquid oxide, even if nonvolatile, could cause poor resistance to oxidation by allowing easy transport of molybdenum and oxygen ions through the oxide. Actually, a sudden increase in the rate of oxidation of molybdenum at 1460°F has been observed to coincide with the appearance of a liquid phase. The formation of a volatile oxide is not unique with molybdenum. The problem is also encountered with vanadium, tungsten, and some of the Pt-Pd group of metals. Vanadium not only forms the volatile V2O3 but, like molybdenum, forms a liquid oxide coating. Few attempts have been made, however, to prevent the rapid oxidation of these metals by alloying. Oxidation of Molybdenum Alloys At the beginning of this work, very little was known of the oxidation resistance of molybdenum alloys. It was known that molybdenum disilicide (with 37 pct Si) has extremely good oxidation resistance,' but this compound is so brittle that it has few uses. It is an effective protective coating for molybdenum when allowance can be made for its brittleness. Chromium was known to retard the oxidation of molybdenum,' but at least 50 pct Cr was necessary to have an appreciable effect. Other, unpublished, reports show that a few other alloys have been given preliminary tests, but the results have not been promising." Choice of Alloys to be Investigated An alloying element might be expected to protect molybdenum in either of two ways: Its oxide might combine with molybdenum oxide to form a stable, nonvolatile complex oxide (a molybdate); or the oxide of the alloying element might form in preference to molybdenum oxide, developing an impervious layer which would prevent the formation of a volatile molybdenum oxide. The knowledge available about the formation of molybdates was meager. Therefore, the initial study was made on alloys of molybdenum with elements having especially stable oxides. On this basis, binary and ternary alloys containing the following six elements were investigated: aluminum, chromium, titanium, zirconium, silicon, and vanadium. Nickel was also added as an alloying element. Although it does not form a more stable oxide than molybdenum, it does impart some oxidation resistance to copper and iron. Its inclusion in the study was fortunate because its alloys proved to be the most promising of those first tested. Apparently nickel formed a stable molybdate. Because nickel was effective in reducing the oxidation rate of molybdenum, the elements iron, cobalt, and tungsten were added to the list. The ten alloying elements mentioned form ten binary and 45 ternary alloying systems with molybdenum. A series of alloys was tested in each of these systems. In addition, at least one test was made on the effect of each of the following alloying elements:

Jan 1, 1957

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine' who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H'-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson'28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By Frederick F. Frick

SPONGE iron as produced at Anaconda is a fine, -35 mesh, impure product, about 50 pct metallic iron, obtained from the reduction of iron calcine at a temperature of 1850°F by use of coke resulting from slack coal. The metallic iron particles are bulky and spongey and precipitate copper readily and rapidly from a copper sulphate solution. Investigation of the treatment of Greater Butte Project, Kelley, ore at Anaconda early showed the desirability of using sponge iron as a precipitant for the copper in solution resulting from desliming of the ore in a dilute sulphuric acid solution. Anaconda had done considerable work on the production of sponge iron in 1914 for use as a precipitant of copper from leach solutions. Some success and considerable experilence were attained at the time. indicating that, sponge iron might be successfully made by a modification of the process used in 1914, a batch process in which an iron calcine was reduced by means of soft coke, resulting from noncoking coal, in a Bruckner-type revolving horizontal cylindrical furnace widely used 50 years ago. The coke and calcide formed the bed in the Bruckner furnace, which was rotated at about 1 rpm. The bed was brought to a temperature of about 1800°F by means of an oil flame over the surface. Although results were reasonably satisfactory, they did not warrant full development of the process at that time. A good deal of work has been done in the last 50 years on the production of sponge iron. The objective in some cases has been the production of a precipitant for copper from solution, but the bulk of the work has been done for the production of open-hearth steel furnace stock. The production of an open-hearth stock presents two problems rather than one: first, producticon of the sponge iron, and second, what is perhaps of equal difficulty and importance, conversion of the sponge iron into a form suitable for use in the open-hearth furnace. So far as is known to the writer, none of the sponge iron processes tried in the past have proved to be economically feasible. However, Anaconda had a combination of conditions appearing to justify an attempt to produce sponge iron which would serve for the leach-precipitation-float process. It was thought that the process used in 1914, if changed to a continuous one, might work out satisfactorily. The following favorable conditions at Anaconda justified the investigation: 1—A sufficient tonnage of good grade iron calcine resulting from the roasting of a pyrite concentrate in one of the acid plants, at substantially no cost. 2—Reasonably cheap natural gas. 3-—The fact that there was no need for production of a high grade product. 4— The fact that there was no need for obtaining a consistently high reduction of' the iron in calcine. A small revolving Bruckner-type furnace about 2 ft ID by 4 ft long was set up for early pilot work at the research building. This pilot furnace showed that a satisfactory product could be obtained at reasonable cost. It also indicated a marked advantage in preceding the reduction furnace with a furnace of similar size and capacity for preheating and roasting out any residual sulphur from the feed. The small furnace was operated for several months, various details of the process were worked out. and sponge iron was produced to supply a pilot LPF plant which treated 300 lb of Kelley ore pel- hr. Later a second pilot furnace 5 ft in diam and 12 ft long inside was set up at our reverberatory furnace building. This furnace confirmed the data of the small furnace and gave a basis for design of the final plant. At Anaconda a pyrite concentrate, running about 48 pct S, is recovered from copper concentrator tailings by flotation. This concentrate is roasted to sulphur of 3 pct or less at the Chamber acid plant. The iron calcine contains about 57 pct Fe and 18 pct insoluble. The iron calcine feed, as mentioned before, is re-roasted and preheated in a reroast furnace preceding the reduction furnace. Both are of the Bruckner type. The reroasted calcine is fed into the reduction furnace at 800" to 1000°F along with 30 pct slack coal. In the feed end of the furnace the volatile is burned from the slack, giving a soft coke which readily serves for reduction of the iron. Hard metallurgical coke will not serve the purpose. since it does not reduce CO readily at a temperature of 1850°F. All indications are that the actual reduction of the iron is accomplished by carbon monoxide below the surface of the bed, which is 30 in. deep at its center. Apparently there is a constant interchange: Fe²O³ + 3CO = 2Fe - 3CO², CO² + C = 2CO Actually iron oxide is reduced by CO at somewhat lower temperature than the 1850 °F used in the process. but this temperature is necessary to obtain a satisfactory rate of furnace production. The furnace atmosphere is generally reducing, and typical blue carbon monoxide flames satisfactorily cover the bed. Gas flames from four 3-in. Denver Fire Clay Inspirator burners are played directly on the bed, which is slowly cascaded by the 1 rpm of the furnace. An excess of coke is necessary to assure maintenance of good reducing conditions in the furnace bed. Part of this coke is recovered for re-use.

Jan 1, 1954

By J. D. Miller, J. E. Sepulveda

Tar sand deposits in the state of Utah contain more than 25 billion bbl of in-place bitumen. Although 30 times smaller than the well-known Athabasca tar sands, Utah tar sands do represent a significant domestic energy resource comparable to the national crude oil reserves (31.3 billion bbl). Based upon a detailed analysis of the physical and chemical properties of both the bitumen and the sand, a hot-water separation process for Utah tar sands is currently being developed in our laboratories at the University of Utah. This process involves intense agitation of the tar sand in a hot caustic solution and subsequent separation of the bitumen by a modified froth flotation technique. Experimental results with an Asphalt Ridge, Utah, tar sand sample indicated that percent solids and caustic concentration were the two most important variables controlling the performance of the digestion stage. These variables were identified by means of an experimental factorial design, in which coefficients of separation greater than 0.90 were realized. Although preliminary in nature, the experimental evidence' gathered in this investigation seems to indicate that a hot-water separation process for Utah tar sands would allow for the efficient utilization of this important energy resource. The projected increase in the ever-widening gap between the domestic energy demand and the domestic energy supply for the next few years has motivated renewed interest in energy sources other than petroleum, such as tar sands, oil shale and coal. Although a number of research programs on the exploitation of national coal and oil shale resources have already been completed, very few programs have been initiated on the processing of tar sand resources in the United States. In recognition of their significance as a domestic energy resource, investigators at the University of Utah have designed an extensive research program on Utah tar sands. An important phase of this program, and the main subject of this publication, is the development of a hot-water process for the recovery of bitumen from Utah tar sands, as a preliminary step toward the production of synthetic fuels and petrochemicals. The term "tar sand" refers to a consolidated mixture of bitumen (tar) and sand. The sand in tar sand is mostly a-quartz as determined from X-ray diffraction patterns. Alternate names for "tar sands" are "oil sands" and "bituminous sands." The latter is technically correct and in that sense provides an adequate description. Tar sand deposits occur throughout the world, often in the same geographical areas as petroleum deposits. Significantly large tar sand deposits have been identified and mapped in Canada, Venezuela and, the United States. By far, the largest deposit is the Athabasca tar sands in the Province of Alberta, Canada. According to the Alberta Energy Resources Conservation Board (AERCB),2,3 proved reserves of crude in-place bitumen in the Athabasca region amount to almost 900 billion bbl. To date, this is the only tar sand deposit in the world being mined and processed for the recovery of petroleum products. Great Canadian Oil Sands, Ltd. (GCOS) produces 20 million bbl of synthetic crude oil per year. Another plant being constructed by Syncrude Canada, Ltd. is expected to produce in excess of 40 million bbl of synthetic crude oil per year. According to the Utah Geological and Mineral Survey (UGMS), tar sand deposits in the state of Utah contain more than 25 billion bbl of bitumen in place, which represent almost 95% of the total mapped resources in the United States.4 The extent of Utah tar sand reserves seems small compared to the enormous potential of Canadian tar sands. Nevertheless, Utah tar sand reserves do represent a significant energy resource comparable to the United States crude oil proved reserves of 31.3 billion bbl in 1976.5 Tar sands in Utah occur in 51 deposits along the eastern side of the state.4 However, only six out of these 51 deposits are worthy of any practical consideration (Fig. 1). As indicated in Table 1, Tar Sand Triangle is the largest deposit in the state and contains about half of the total mapped resources. Information regarding the grade or bitumen content of Utah deposits is still very limited. The bitumen content varies significantly from deposit to deposit, as well as within a given deposit. In any event, the information available6-8 seems to indicate that Utah deposits are not as rich in bitumen as the vast Canadian deposits which average 12 to 13% by weight.9 Although many occurrences of bitumen saturation up to 17% by weight have been detected in the northeastern part of the state (Asphalt Ridge and P. R. Spring), the average for reserves in Utah may well be less than 10% by weight. Separation Technology As in any other mining problem, there are two basic approaches to the recovery of bitumen from tar sands. In one

Jan 1, 1979

By R. E. Reed-Hill, W. H. Hartt

The "(3034) " twin lamellae in magnesium have been reexamined using electron microscope replicas. The double twinning sequence (1011)- (1012) for these lamellae has been reconfirmed. Evidence is presented showing that the irrational habit of these twins is probably the direct result of a need to accommodate the second-order twinning shear. This accommodation vesults in both an external shear in the matrix and an internal shear in the lamella. A model is presented which accounts for the experimental obseruations. HCP metals are generally characterized by strong textures in which the basal planes of the grains tend to be aligned parallel to the rolling direction in sheet or plate and to the axis of wires and rods. Since these directions are normally those in which finished products may be subjected to uniaxial tensile stress, these textures effectively place the crystals of magnesium objects in orientations unfavorable to both basal slip and {1012) twinning, the easily activated deformation systems of this metal. However, when magnesium crystals are deformed near room temperature by a tensile stress nearly parallel to the basal plane, another mode of deformation can occur.',2 This is _a double twin which forms first by twinning on {loll), followed by retwinning on (1012). The resulting twin lamellae are of considerable interest. First, they can be responsible for "brittle fracture''; when a tensile stress axis lies in the basal plane, because the reoriented crystal structure of a lamella is well-aligned for slip while the parent crystal is not. Extensive internal deformation may thus occur while the matrix is still almost undeformed. This deformation can produce a ductile rupture running the length of the twin.3 Complete failure of the specimen may then oc-cure by the spreading of cracks from one twin lamella to another, or by the movement of a crack into a grain boundary and then along grain boundaries. Since the the volume fraction of these doubly twinned elements is normally very small, the fracture may be classed as brittle, although the fracture mechanism is, of itself, essentially ductile. It is quite probable that the ductility transition, normally observed4 in magnesium at or slightly Obove room temperature, is closely associated with these second-order twins. The detailed relationship of these twins to fracture in single crystals will be the topic of another paper. The present paper is concerned with a second important aspect: the irrational habit of these double twins that falls close to {3034), or approximately 7 deg away from the primary (10il) twin habit. There is good reason to believe that this habit results directly

Jan 1, 1968

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE complicated nature of the property changes that accompany age-hardening has made it necessary to reconsider and to elaborate the simple dispersion theory.1 It has been apparent for some time that more direct information is needed concerning the atomic mechanism of precipitation from solid solution if the theory of age-hardening is to be developed past a purely qualitative stage.‡ Fortunately, in recent years information has been developed which allows us to trace in detail the lattice changes accompanying the process of precipitation from solid solution. This information relates chiefly to the sequence of the several stages of lattice alteration by which the matrix lattice is transformed to the equilibrium precipitate lattice, and permits reasonable inferences to be drawn concerning the states of internal strain that accompany these stages. This information is most complete for the solid solution of copper in aluminum. The equilibrium precipitate is the ?' phase," CuA12." This forms in plates, parallel to the {100} matrix planes. The atom pattern and atom spacing on the plane in ?' lying parallel to this plane are roughly similar to those opposite it in the matrix.' The formation of ?', however, is preceded by the formation of a transition lattice ?', which again lies parallel to the matrix {100} plane, but in this case the matching of atom pattern and spacing across the matrix-precipitate interface is nearly perfect; thus there is lattice coherency across the interface and the interface is a plane of separation in only a very limited sense.4-8 Particles of ?' may be recognized microscopically and form a well-defined Widmanstätten figure.* The ?' lattice is recognized by the occurrence of diffraction lines on powder photograms or of spots on Laue photograms which may be analyzed in the usual ways to determine the lattice type and the lattice spacings. Very recent research 6.7,1 has shown, however, that streaks occur on the Laue photogram at an earlier point in time during the aging process. These streaks have been attributed to a preferential clustering of copper atoms into small platelike elements of only a few atoms in thickness and a few hundred atoms in diameter, probably of the composition of "CuA12," which may be designated as Guinier-Preston zones or aggregates.1 It is difficult if not impossible to determine the lattice type and lattice spacing in these aggregates. It is possible1 that these aggregates are in fact merely ?' in a high state of dispersion; the inclination to argue this is strong, as we shall see later. Never-

Jan 1, 1941

By R. F. Mehl, B. Lustman

THE formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.1 It is necessary here only to enumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type-i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained-the isothermal growth of the phase follows a simple parabolic equation: [1 = ki [I]] where X is the thickness of the alloy layer, k the reaction rate constant, and [t] the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.3 In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varies with temperature according to the Arrhenius equation: [k = Ae-QIRT [2]] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942