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By W. T. Ober

the hammering effect acts only to a point 3 in. back from the cutting edge, and the hardening heat extends back only 1 in. from the cutting edge. Then, as a steel is taken from the fire, the grain condition is as shown in Fig. I. After the forging operation has been performed the condition shown by Fig. 2 exists. The heating operation to harden the cutting edge produces the effect shown in Fig. 3. The questions that naturally arise are: Will the cost of the extra heat treatment necessary to change this condition (annealing) be more than the saving that may be effected in the drill steel or will the extra heating be an economical as well as a wise thing to do? Is this condition necessarily detrimental to the maximum service of the drill steel? Can this annealing action be obtained in the hardening heat by heating more of the bit, say at least 5 in., to the hardening temperature but quenching only the end of the bit by a shallow immersion? Short Rock-drill Steels Reclaimed by Welding By W. T. Ober, Lynn, Mass. Experimental tests by the Thompson Company have shown that short lengths of rock-drill steels may be reclaimed by electric butt welding. The drills used in the experiments were hollow drills l1/4-in. in diametcr containing 0.95 per cent. to 1.05 per cent. carbon. The ends to be joined must first be ground off fairly square and the greater part of the rust, scale, etc. removed for 3 or 4 in. back in order to insure good electrical contact with the dies of the welder and countersunk, with an 80° countersink, approximately 1/4 in. The steels are then clamped in the copper dies of the welder, so that a length projects from the inside edge of each pair of dies equivalent to from one-half to three-quarters the diameter of the drill. The drills should also be brought into accurate alignment. The first step is to bring the ends into close proximity and then close the primary circuit of the transformer, slowly bringing the steels together until their ends lightly touch, when they will "flash," that is, minute

Jan 1, 1922

By W. T. Ober

the hammering effect acts only to a point 3 in. back from the cutting edge, and the hardening heat extends back only 1 in. from the cutting edge. Then, as a steel is taken from the fire, the grain condition is as shown in Fig. I. After the forging operation has been performed the condition shown by Fig. 2 exists. The heating operation to harden the cutting edge produces the effect shown in Fig. 3. The questions that naturally arise are: Will the cost of the extra heat treatment necessary to change this condition (annealing) be more than the saving that may be effected in the drill steel or will the extra heating be an economical as well as a wise thing to do? Is this condition necessarily detrimental to the maximum service of the drill steel? Can this annealing action be obtained in the hardening heat by heating more of the bit, say at least 5 in., to the hardening temperature but quenching only the end of the bit by a shallow immersion? Short Rock-drill Steels Reclaimed by Welding By W. T. Ober, Lynn, Mass. Experimental tests by the Thompson Company have shown that short lengths of rock-drill steels may be reclaimed by electric butt welding. The drills used in the experiments were hollow drills l1/4-in. in diametcr containing 0.95 per cent. to 1.05 per cent. carbon. The ends to be joined must first be ground off fairly square and the greater part of the rust, scale, etc. removed for 3 or 4 in. back in order to insure good electrical contact with the dies of the welder and countersunk, with an 80° countersink, approximately 1/4 in. The steels are then clamped in the copper dies of the welder, so that a length projects from the inside edge of each pair of dies equivalent to from one-half to three-quarters the diameter of the drill. The drills should also be brought into accurate alignment. The first step is to bring the ends into close proximity and then close the primary circuit of the transformer, slowly bringing the steels together until their ends lightly touch, when they will "flash," that is, minute

Jan 1, 1922

ALABAMA. Aldrich, Aldrich, W. F. Anmston, Noble, A. E Bessemen, Abbott, C E, Fergusson, V Birmingham, Aldrich, T. H, Aldrich, T. H, Jr, Bowron, J, Burbidge, T A, Collord, G L, Crockard, F H, Davis, F H, Dimmick, F. D., Hiller, E., Johnson, G R, Ludwig, C P., McCormack, G B., McCrery, Peters, R , Jr , Phillips, W B, Ramsay, E ,Shook, A. M Car bon Hall, Pill, J R Emsley, Williams, E P Gadsden, Hudson, J B , Helena, Squire, J Holt, Shook, J W. Huntnnlle, Moss Lehigh, Toulmin. Rock Run, Garvin, J. M. Sheffield, Miller, D I Tusscaloosa, McCausland, E J , Woodward, Woodward, A. H

Jan 1, 1910

By N. O. Gray, John Henderson

Hydrogen-reduction data for naturally occurring single crystals and Prepared polycrystals of dense hematite have been presented. Results cover the temperature range 400o to 1000oC, for particles from ten sources, ranging in size from 0.07 to 10 mm and in shape from spheres to cylinders, cubes, and thin slabs. A consistent pattern of behavior has been demonstrated for single crystals and the reduction mechanism shown to be temperature-dependent. Below 579oC reduction is a simple topochemical process but at higher temperatuves it is complex and occurs in two distinct stages. Prepared particles from these laboratories behave in a similar manner to the single crystals. Data from two investigators showing topochernical reduction of Prepared particles above 575°C are inconsistent with that for other dense hematites. It is concluded that topochenzical reaction should not be used as a model for generalized rate expressions for dense hematites. SINCE 1958, McKewan1-6 has brought to prominence a simple concept of dense hematite reduction. This model is that oxygen is lost from a hematite particle undergoing reduction only from an oxide-iron interface that recedes in such a way that the oxide remaining retains the original shape of the particle, i.e., reduction occurs topochemically. An adjunct to this concept is that any intermediate oxides in the transition from hematite to iron only form thin layers so that oxygen cannot be lost from the particle without movement of the oxide-iron interface. Further, the rate of oxygen loss from the particle is said to be proportional to the area of the receding interface so that the iron layer grows linearly with time and the over-all reduction process can be described by the equation where ro and do are the initial particle radius and density, respectively, R is the fraction of the original oxygen lost, i.e., the fractional reduction, at time t, and K is the rate constant. The idea of an underlying simplicity in hematite reduction is attractive because it gives a tractable basis from which general theories of hematite reduction can be developed and it has received wide support,7-14 based mainly on the large amount of data13 that can be fitted to Eq. [I]. However, despite the fact that this equation has been derived for dense materials, the bulk of the data that have been used to test it13 have been for materials of only about 90 pct of theoretical density (5.26 g cm-3) or less, so that its generality for dense hematites has not been demonstrated. In any case, as will be seen, adherence of reduction data to Eq. [1] does not necessarily imply that reaction occurs topochemically. In this work only data for hematites approaching theoretical density are considered and it will be shown that in only one study besides McKewan's is topochemical behavior observed over the whole range of temperature investigated. For the majority of materials a linear rate of interface advance is observed to complete reduction only when wustite is not a stable intermediate phase in the transition of hematite to iron, i.e., at temperatures below about 575°C. Above this temperature, reduction is an exceedingly complex series of reactions that takes place in two distinct stages and it is only in the first stage that reaction in any way resembles a topochemical process. This means then that, far from representing general behavior as has commonly been supposed, topochemical reaction for dense hematites is only a particular behavior that may be observed under some circumstances. EXPERIMENTAL Hydrogen-reduction data have been collected and cross-checked in these laboratories by three techniques, weight loss, collection of water evolved in the reduction reactions, and direct metallographic examination. Details of these techniques are discussed elsewhere," where it is shown that results obtained by the three methods are in close agreement. The weight-loss method, by which most of the results were obtained, consisted of hanging the sample in a platinum mesh basket from an Ainsworth Model AV-AU-1 vacuum recording balance inside a vertical l 1/4-in.-ID alumina tube furnace. Dry deoxidized hydrogen was flowed downwards through the tube at 2 to 4 liters min-1 (stp). Single crystals from two sources and artificial oxides from three sources have been examined. The single crystals were from hematite deposits at Yampi Sound, Western Australia, and Brazil, the latter being obtained from Gregory, Bottley and Co., London, U.K. The "Yampi Blue" crystals were hand-picked from washed, magnetically concentrated, sized fractions, -200 mesh BSS (mean diameter ca 0.07 mm) and —36 + 44 mesh BSS (mean diameter ca 0.4 mm) while 10-mm cubes were cut from the Brazilian crystals with a diamond saw. The starting materials for the prepared particles were hematites designated, respectively, "Specpure Iron Oxide", Laboratory No. S639 from Johnson Matthey & Co. Ltd., London, U.K., "Calcined Ferric Oxide" from B.D.H. Laboratory Chemicals Division, Poole, U.K., and "Pigment Grade Oxide", EPR-50, from C. K. Williams & Co., Easton, Pa., U.S.A. Approximately spherical particles were prepared from the artificial oxides by rolling the material, moistened if necessary, in a glass jar, and cylindrical compacts approximately 10 mm in diam and of approximately equal height were pressed in a steel die at 200 psi. These spheres and cylinders were subsequently fired in oxygen for 20 to 100 hr at 1370°C. The

Jan 1, 1967

By Paul A. Schafer

BALATOC mine, the principal gold-producing mine in the Philippines, is 10 miles southeast of Baguio, in the Cordillera Central of northern Luzon.1 The region is a deeply dissected plateau, ranging in altitude from 3000 t0 5000 ft. above sea level. The rocks consist chiefly of granodiorite, diorite, and remnants of metamorphosed sediments, cut by dikes of andesite porphyry and quartz-diorite porphyry. All are intruded by a volcanic breccia plug, oval in horizontal section, about 3200 ft. long and 2300 ft. wide, which is the north central part of the mineralized area. Three main vein systems have been developed (Fig. 1): q6, 231 and 364, which strike about N.70°E. and dip 5o to 90°S. Each system is a braided zone consisting of many individual components. They are disturbed by a series of premineral faults or shear zones striking about N.45°E. Twelve of these produce important effects on the persistence, character, and quality of veins. From west to east the faults are named (after claims): Hog, Big Gun, Bull, Pine, Lolita, Bar No. I, Bar No. 2, Curt, Sun, Helen, Itoe, and Frog. They are early breaks formed prior to the N.70°E. vein fractures. Mineralization occurs on them but, with several prominent exceptions, they are too low grade to mine. A number of northwesterly striking faults complete the structural pattern. Although they are relatively abundant, the effect on the veins is so small that they do not present any problems in mining or development. All of these faults that have been observed are later than the N.70°E. veins and offset them to the left. NORTHEAST FAULTS The early northeast faults* are notably continuous in spite of their small displacements, 20 to 100 ft. Frequently they appear so weak that their importance is masked and their identity clouded. The gouge along any of these faults may vary from exceedingly weak at one point to very strong at another point only a short distance away. In other words, the amount of gouge depends on the changes of attitude of the fault plane, and is no indication of the extent of the movement. Places where walls are spread apart are filled with gouge squeezed from tight places. Also, mineralization sometimes obscures fault gouges by replacement. The mineralization of northeast faults has produced several important ore bodies; namely, 231 west on Pine fault and q6 vein on the same fault. To a smaller extent, Lolita, Curt, Bull, Bar No. I, and Sun

Jan 1, 1942

By J. B. Newkirk, A. H. Geisler

INTRODUCTION CERTAIN of the permanent magnet alloys provide ideal systems for the study of the kinetics of the precipitation reaction and the correlation of structure with properties. One such system, Cu-Ni-Fe, was found by Bradley1,2 to exhibit a coherent transition state in the precipitation process analogous to that reported for Al-Cu alloys somewhat earlier.3 The attractiveness of some permanent magnet alloys for study lies in the fact that vertical sections of the ternary phase diagram in certain regions of composition (Fig I) have as their prototype the binary Ni-Au diagram. Alloys of this type decompose into products that have the same crystal lattice type but only slightly different lattice parameters. The advantages that such alloy systems offer for study over the usual in which an intermetallic compound is formed are many: I. Since the precipitate has the same crystal structure as the matrix, complex atomic movements are not required to form the new lattice. 2. Similarly, complex orientation relationships are not involved for both the matrix and the precipitate would be expected to have the same orientation. 3. Small disregistry of the decomposition products at equilibrium (in contrast with Cu-Ag alloys) is conducive to extensive coherent growth in the transient state and thus the transition lattice can be detected by the usual X ray diffraction methods. 4. Finally, the relative quantities of precipitate and depleted matrix can be varied from o to 100 pct* thus permitting wide freedom for the study of the effect of composition on coherent growth and properties. In the Cu-Ni-Fe alloys of appropriate composition, the face-centered cubic precipitate and also the depleted matrix when first formed are coherent with the parent matrix.1,2 The two have the same [ao] parameter as the original matrix but they are both tetragonal; the precipitate has an axial ratio c/a < I while that of the depleted matrix is c/a > I. When coherency is lost they assume the normal face-centered cubic structure with the depleted matrix having a lattice parameter greater than the original matrix and that of the precipitate less. Such a mechanism would also be expected for Cu-Ni-Co alloys because of the similarity in constitution but this had not been demonstrated. The present investigation was conducted on a Cu-Ni-Co alloy. The constitution diagram and magnetic properties of these alloys have been fairly well established 4,5 however, no previous determinations of mechanism of precipitation and no correlation of structure with properties had been made. Thus, an alloy of this system was chosen for a comprehensive investiga-

Jan 1, 1948

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

THE National Safety Council will hold the following ses-sions in the Waldorf-Astoria Hotel, New York, N. Y., on Oct. 2, 3 and 4: Oct. 2. 9.30 A. M. 1. Report of past year committees, by Chairman 2. "Safety Pays," by Howard I. Young, Vice-President, American Zinc, Lead and Smelting Co., Mascot, Tenn. (Discussion) 3. Entertainment 4. "Methods and Results of Improved Foremanship Conferences," by H. A. Gilbertson, Director of Per-sonnel, Lehigh Coal and Navigation Co., Lansford, Pa. (Discussion) 5. Appointment of election and resolutions committees Oct. 3, 9.30 A. M.

Jan 9, 1928

By Frank Harwood Riddle

Products made from the ores of the sillimanite group, and synthetic substitutes for them, have unique properties, and service tests prove that they are playing, and will continue to play, a major part in improvements in metallurgical processes. Also, they are examples of how comparatively useless, rare, or "museum" minerals have been made available in commercial quantities. Until research developed uses for them, the minerals had been observed only in small, scattered masses, or crystals. Improvements in ceramic processes and compositions have come about very gradually. In the last 10 or 15 years, several outstanding developments have been made. Of greatest interest to the mining and metallurgical engineers are those affecting the composition, necessitating the mining of new minerals, and improvements in ceramic products used in metallurgical processes. Sillimanite and Mullite Sillimanite (Al2O3.SiO2), then known as Fibrolite, according to Dana,&apos; was first reported in 1792. In 1796, cyanite (Al2O3.SiO2) was first described.2 In 1873, Behrens published results of his microscopic study8 of porcelain. He showed that it contained what appeared to be crystals, which dissolved less readily than quartz and glass in hydrofluoric acid. Hussak4 described the presence of needlelike crystals as occurring in some instances in small amounts in certain porcelains. In 1908, Plenske and Zoellner both studied porcelain structure.5 Plenske observed that "sillimanite" might be present in masses of exceedingly minute grains which apparently were amorphous. Zoellner advanced the theory that the needlelike crystals were formed by a molecular change in the clay,

Jan 1, 1932

By C. S. Barrett, A. Smigelskas

J. T. NORTON*—I think Mrs. Smigelskas Fischer has done a splendid job in working out the pole figures from rather difficult photograms which are common to beryllium. Is there not a mistake in Fig 2 in that the pole figures B and C have been interchanged? A. SMIGELSKAS FISCHER (authors&apos; reply)—Yes, there is such an error in the labeling of the pole figures of Fig 2. The correct plane for Fig 2b and 2c is the plane in parenthesis above the figure numbers and not that in the figure subtitle. J. T. NORTON—Also, I would like to mention another method of obtaining the data for pole figures which would be particularly applicable to this problem. It is a method which has been published only

Jan 1, 1950

By Charles R. Keyes

PAGE I. Introductory............ 140 II. Location and History...........140 III. Surface-Relief of the District....... 141 IV. General GeoloGic Features........ 142 1. Main Relationships and Map....... 142 2. Résumé of Geologic History..143 V. Geologic Formations Represented...144 1. Broader Considerations......... 144 2. Geologic Section.......... 145 3. Nomenclature.......... 146 4. El Pasan Limestones..146 5. Santa Rita Limestone.... 146 6. Silver Shales........... 147 7. Bella Shales........... 147 8. Berenda Limestone..147 9. Grande Limestone... 148 10. Lake Valley Limestone........ 148 11. Sierra Limestone.......... 149 VI. Unconformities........... 149 VII. Geologic Structure.......... 150 1. Main Characteristics......... 150 2. Folding........... 1.50 3. Faultings........... 150 4. Relations of the Eruptives...153 VIII. Geologic Relations OF the Ore-Bodies...... 154 1. Governing Factom......... 154 2. Position.......... 154 3. Relations to Foldings...155 4. Relations to Lines of Dislocation... 15.5 5. Relations to Present Surface.Relief..156 6. Relations to Eruptive Rocks...157 7. Relations to Lithologic Nature of the Rocks.... 158 IX. MINERALOGIC CHARACTER OF THE ORES...... 158 X. Origin of the Ore.Deposits..159 1. General Statement......... 159 2. Original Source of the 0re.Materials...160 3. Contact-Metamorphism of the Region... 161 4. Process of 0re.Concentration..162 5. Lowering of Ground-Water Level..162 6. Formation of Cerargyritic Ores...163 XI. Recapitulation........... 168

Jan 1, 1909

By H. R. Ogden

The notch sensitivity of titanium alloys is affected by impurity content, microstructure, and heat treatment. Using notch tensile properties to evaluate notch sensitivity, three commercial titanium-base alloys were investigated over the temperature range of -320o to 390°F. The alloys studied were Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo. Six interstitial levels were studied for each alloy in four mi-crostmctural conditions. The ff- 0 alloys were studied in both the annealed and heat-treated condition. All tests were conducted using 1/4-in. diam round tensile samples. The notched samples had a 50 pct notch with a notch sharpness (a/r) of 53, corresponding to Kt 6.3. Notch sensitivity was increased by increased interstitial content, low temperature, and acicular-type microstructures. The heat-treated, high-interstitial content - 13 alloys were more notch sensitive than the same alloys in the annealed condition. In addition, minima in the notch tensile-temperature curves were observed at temperatures near 32°F. These minima became more pronounced with increasing interstitial content. 1 HE increaseduse of titanium alloys in high strength applications at subzero temperatures requires that a better under standing of the low-temperature behavior of the alloys be obtained. At low temperatures, metals generally exhibit increased strength with lowered ductility and tohness. Notch sensitivity and the factors which influence it become more important as the strength level is increased and the temperature is decreased. Some of the factor s which affect notch sensitivity in ti- tanium alloys are composition, interstitial content, microstructure, and heat-treatment condition. In this paper, the results of a study of these variables on the notch sensitivity of three titanium alloys at temperatures from —320o to 390o are reported. The notch geometry selected for this program was chosen to provide a severe test of notch sensitivity. The ability of the metal to flow without initiating fracture under these severe conditions is reflected in the notch-strength values. Since notch strength is, in part, determined by the constraint exerted by the combined tensile stresses, the behavior of notch specimens reflects the properties of the material under combined stresses. For example, a material with a high notch-unnotch strength ratio may be expected to withstand the biaxial stresses encountered in a pressure vessel better than a material with a low ratio of notch-unnotch strengths. This implies that maximum strength alone is not a sufficient criterion for applications of this type. It further may be concluded that the various conditions that promote poor notch behavior also will affect adversely the performance of materials under combined stresses. In the alloys studied, these included low temperatures, high interstitial levels, and hasformed microstructures. EXPERIMENTAL PROCEDURES Three alloys, Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo, were purchased from commercial producers as 2-in.-dam rod stock. Oxygen and nitrogen were added to these alloys by remelting to obtain a variety of interstitial contents as shown in Table I. In order to Compensate for the much more potent strengthening effect of nitrogen compared with oxygen, an oxygen equivalent content is used to describe the total oxygen plus nitrogen contents studied. It has been suggested previously1 thatnitro-gen is approximately twice as effective in strengthening as oxygen, and carbon, to the extent it is in so-

Jan 1, 1962

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth&apos; infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.&apos; A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) &apos;206, pp. 257-263; Journal OF Metals (February 1956).

Jan 1, 1957

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller&apos; parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green&apos; dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.&apos; As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K&apos;. Making these changes.

Jan 1, 1942

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10&apos; to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

The following is an incomplete list of members and guests who called at Institute headquarters during the period Oct. 10, 1919, to Nov. 10,1919. Carl A. Allen, Salt Lake City, Utah. W. G. Mitchell, Montreal, Canada. M. M. Altmayer, Paris. Henry S. Munroe, Litchfield, Conn. A. E. Bellis, Major Ord., Springfield J. S. Negru, New York, N. Y. Armory, Springfield, Mass. Edmund Newton, New York, N. Y. R. S. Botsford, New York, N. Y. A. W. Newberry, Cleveland, Ohio. Henry S. Burnholz, Monterrey, Mexico. C. C. O&apos;Harra, Rapid City, S. D. D. E. A. Charlton, New York, N. Y. Fred S. Porter, Philadelphia, Pa. C. C. Colburn, Denver, Colo. Donald A. Powell, Columbus, Ohio. C. V. Corless, Coniston, Ontario. Thomas T. Read, Washington, D. C. I. N. Daily, Seattle, Wash., W. L. Remick, Chrome, N. J. E. V. Daveler, Butte, Mont: Hallet R. Robbins, San Francisco, Calif. John Davis, Fairbanks, Alaska.&apos; Milnor Roberts, University Station, E. W. Engelmann, Salt Lake City, Utah. Seattle, Wash. M. E. Erdofy, New York N. Y. Thos. S. Roberts, Lakehurst Proving W. F. Ferrier, Toronto, Canada. Grounds, N. J. H. A. Fisher, Pittsburgh, Pa. George B. Rodgers, Dobbs Ferry, N. Y. Walter Fitch, Sr., Eureka, Utah. John C. Rogers, Copper Cliff, Ontario. C. D. Grier, New York, N. Y. Joseph L. Rosenmiller, Bethlehem, Pa. A. Hibbert, London. . C. J. Saville, Portland, New South Wales. John E. Hodge, Minneapolis, Minn. W. A. Scheuch, New Jersey. W. E. Hopper, Newark, N. J. S. B. Shutts, Lynchburg, Va. M. R. Hull, McGill, Nev. E. W. Smith, U. S. Army. A. W. Ibbett, Trinidad, B. W. I. S. J. Speak, London. A. O. Ihlseng, Joplin, Mo. John. B. Stewart, Santiago de Cuba, Sherwin F. Kelly, Lawrence, Kans. Cuba. R. G. Knickerbocker, Logansport, Ind. S. A. Taylor, Pittsburgh, Pa. .M. H. Kuryla, Eureka Colo. Karl Thomas,&apos; New York, N. Y. F. G. Lasier, Detroit, Mich. F. L. Torres, Eureka, Nev. David Lasuer, Elizabeth, N. J. Henry Traphagen, Toledo, .Ohio: H. H. Lauer, Allentown, Pa. W. D. Van Doren, Ottawa, Canada. J. Whitney Lewis, Care First Nat&apos;l Bank, J. A. Vernon, Newport, R. I. Tulsa Okla James Wilding, San Francisco, Calif. James W. Love, Knoxville, Tenn. D. J. Williams, Butte, Mont. Dorsey A. Lyon, Washington, D. C. Harry J. Wolf, New York, N. Y. M. E. Martiner, Boston, Mass.. Dwight E. Woodbridge, Duluth, Minn. Benj. L. Miller, Bethlehem, Pa. Percy E. Wrighn, Seattle, Wash. W. G. Miller, Toronto, Canada. F. Yamada, Tokyo, Japan.

Jan 12, 1919

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts&apos; law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts&apos; law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

By E. Miller, R. Geffken, K. L. Komarek

The thermodynamzc properties oJ liquid Cd-Sb alloys were investigated using the cell arrangement measurments were obtained every 2°C at a heating and cooling rate of 12°C per hr and at equilibrium every 2O0C frorn 500°C down through the stable liquidus. The S-shaped asCd US composition curve was used in the cotnposition regzon near Cd,Sb, to calculate a tempeerture-dependent inleraction coefficient from quasichemical theory. Rapid changes in a scd were observed at a transition temperature varying from 400" to 465°C depending on con/kosition. It could not be determined if the changes in aScd were discontinuous, but tlze composition dependeke of the magnitude of the change is indicative of a second-order phase transformation in the liquid. The values of the experimental changes in ASCd are in agreement with calculations from the slope of the transition temperature, using the concept that a second-ovdev phase transition occurs in liquid Cd-Sb alloys. II is suggested that the transformalion is associated with the formation of Cd4Sb3 molecules in the liquid. ThE structure of liquid alloys is the subject of many investigations. X-ray, resistivity, and thermody-namic data have been interpreted as indicating varying degrees of short-range order in the liquid in alloy systems forming inter metallic compounds. In general, the melting process is not a transition from an ordered to a completely disordered state, but some degree of order is retained in the liquid. Maximum ordering in the liquid state occurs close to the melting temperature of the compound and the arrangement of atoms becomes more random at higher temperatures. Of special interest in this respect is the Cd-Sb system. It is one of the few metallic systems which form both stable and metastable compounds when liquid alloys are cooled at normal rates. The stable system exhibits an intermetallic compound, CdSb, melting at 459"c.l A second compound, CdrSbs, has also been reported,&apos; melting close to this temperature. The metastable system has one compound, CdsSbz, melting at 420"c.I Resistivity measurements on liquid Cd-Sb alloys close to the liquidus temperatures have been interpreted in terms of a complex ordering behavior which changes rapidly with increasing temperature.3 The resistivity-composition curve is characterized by two maxima corresponding in composition to CdSb and CdsSbz. The resistivity-temperature plots show sharp breaks for alloys in the composition range of 45 to 70 at. pct Cd on cooling through a transition temperature close to the stable liquidus. Fisher and phillips4 investigated the influence of temperature and composition on the viscosity of liquid CdSb alloys. The viscosity of some alloys increases sharply on supercooling below the stable liquidus. A maximum in the viscosity-composition curve occurs at the composition CdSb. The thermodynamic properties of liquid Cd-Sb alloys have been investigated by Seltz and ~e~itt&apos; and Elliott and chipmane by the electromotive-force method and their results are in good agreement. However, these investigations were carried out at temperatures well above the liquidus temperatures of the alloys, and the temperature coefficients of the electromotive force, dE/dT, were obtained from experimental points for each alloy at a few temperatures considerably above the liquidus temperature. Scheil and ~aach&apos; investigated the thermodynamic properties of this system by the dew point method in the temperature range from about 100°C above the stable liquidus down into the supercooled liquid region. They reported several anomalies, i.e., the activity of a melt on heating differed from that on cooling, and the activity increased sharply in the limited temperature interval immediately above the liquidus temperature of the stable alloy, followed by a sudden decrease below the liquidus. Values obtained on heating and cooling were not in agreement. A reinvesti-gation of a few alloys by Scheil and Kalkuhl&apos; by the electromotive-force method failed to confirm these observations. The authors concluded that the anomalies were due to inhomogeneities in the starting alloys and they discarded their previous results. The present investigation was undertaken in order to obtain thermodynamic data close to the liquidus temperature and in the supercooled region where the anomalies were originally reported, employing the electro motive-force method. This method is quite precise and will most easily permit observations of small changes in activity and partial molar entropy with temperature. Measurements were taken every few degrees so that the dE/dT values could be calculated over the entire temperature range and small changes in the thermodynamic properties close to the liquidus temperature could be observed. I) EXPERIMENTAL PROCEDURE Specimens were prepared from 99.999+ pct Cd and Sb (Cominco). Surface oxide was removed by scraping and then melting the metals under vacuum and filtering through Pyrex wool. Appropriate amounts of the metals were weighed on an analytical balance to k0.1 mg, sealed in double Pyrex capsules under vacuum,

Jan 1, 1968