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By Paul Rhedey

Various commercial pelroleum cokes were heat-1,reated at temperatures between 500° and 1500°C, in a nitrogen atmosphere, in laboratovy induction furnaces. The rate of tenlperature rise was varied betzveen 10" and 300°C per min, or the green cokes were flash-calcined, orv a combination of heating rates was used. Changes in the rate of heating had only negligible effects on the degree of' calcination as characterized by mean crystallite thickness and the chemical properties of the calcined coke. The physical structure of the cake was however significantly affected when rate of heating during calcination exceeded 50°C per min over the temperature range of 600° to 900°C. Surface-accessible porosily increased with the .rate of temperature rise, and this was accompanied by a change in pore size distribution. Source and properties of the green coke also had an influence on the structure of the calcined coke. The evidence presented suggests a similar mechanism of porosity development in petroleuiiz coke during calcination in industvial equiplnenl, such as rotary kilns. An increase in surface accessible povosity incveased the pitch binder requirement when the coke was used as aggregate in Soderberg paste. A correlation was established between calcined coke porosity and paste binder requiremenl. ManY results have been published on the changes of properties of petroleum coke during calcination, such as chemical composition, real density, electrical resistivity, crystallite and pore structure. The correlation of these properties with temperature of calcination and time at maximum temperature has been rather well established in both laboratory and pilot plant experiments. Surprisingly little attention has been given however to the effect of calcination conditions, such as rate of temperature rise or furnace atmosphere, on the chemical and structural properties of the calcined coke. It has been observed that petroleum coke, when calcined in industrial equipment, acquires higher porosity and lower real density than those attainable in laboratory furnaces at apparently identical calcina- tion temperature and soaking time. This paper describes a study of the effect of rate of heating during calcination on calcined coke properties using green petroleum cokes of different volatile matter, hydrogen, and sulfur content. An attempt was made to correlate the changes in coke structure with the flowability of anode paste of the type normally used in aluminum reduction cells. EXPERIMENTAL Petroleum Cokes Used. In the study of release of volatile matter and sulfur during calcination and the effect of rate of heating on calcined coke properties two delayed cokes of different sulfur contents were used. The results of analysis of the green cokes are given in Table I. In the study of the effect of flash calcination thirty-six commercial petroleum cokes from twelve different refineries were used with a range of properties shown in Table 11. Calcination Conditions. Calcination experiments were carried out in a laboratory induction furnace. In each run a 200-g sample of dry green coke sized to 10 by 65 Tyler mesh was calcined in a graphite crucible. The crucible containing the sample was placed in the middle of a stack of eight others filled with metallurgical coke to reduce temperature gradients within the sample. Temperature was measured by two Pt, Pt-10 pct Rh thermocouples and controlled by a Celectray instrument. The two couples generally agreed within 5°C. In the study of volatile matter and sulfur release the samples were heated to temperatures in the range of 500" to 1500°C at a rate of 10°C per min in a nitrogen atmosphere and held at the final temperatures for 30 min. In the study of the effect of heating rate on calcined coke properties the desired rates between 10' and 300°C per min were obtained by manually adjusting the power input. Flash calcination was carried out by dropping 100 g of the green coke into the graphite dish preheated to the calcination temperature. Because of the small heat capacity of the furnace the coke was introduced in 20-g portions at a time. For this purpose a 2-in.-long nipple between two 1-in. gate valves installed on the top flange of the furnace served to provide a gas seal while feeding coke to the furnace. It was estimated that the temperature of the coke reached that of the furnace at a rate of approximately 1000°C per min. Holding time at final temperature was also 30 min. Calcined Coke Proper- Determined. Porosity was determined on 20 by 35 Tyler mesh samples using an Aminco-Winslow mercury pressure porosimeter with an operating range of 1.8 to 3000 psi absolute pressure (100 to 0.05 p pore diameter range).' Apparent density was obtained by the mercury poro-simeter. It represents a particle density of the 20 by

Jan 1, 1968

By W. A. Eardley

FIFTEEN years ago the world's deepest oil well penetrated the earth about 7300 ft. That depth has now been more than doubled. Why has such deep drilling become necessary and how has it become possible? Three factors have had an important bearing: (1) Depletion of shallow zones, making it necessary to search for deeper producing measures. (2) The perfection of prospecting methods, which have been success- fully used to locate favorable buried structures, many at great depth. (3) Improvement in the quality of steels used for drilling.

Jan 1, 1940

By S. S. Arentz

An organized safety program has reduced accidents at Pioche because effort is first devoted to arousing and maintaining interest in safety, followed by training in accident prevention, assigning responsibility for the detection and removal of safety hazards, and finally, by keeping score through an adequate system of records. A health program is intergrated with the safety program.

Jan 1, 1950

By A. H. Geisler, J. H. Keeler

Preferred orientations in rolled and annealed titanium sheets were determined by the Geiger counter spectrometer X-ray diffraction technique. Five annealing textures dependent upon the temperature range of annealing were found, and in order of increasing annealing temperature pendent upon the temperature range are: 1—a deformation like texture, 2—a rotated inorder a-recrystallization temperature texture, 3-a retained u-recrysraIlization texture, on annealing at lower temperatures of the ß-region, 4—a transformation texture based on recrystallized a and predicted by the Burgers' relationship, and 5—a ,ß-cube texture. These results are examined in terms of current theories of recrystallization textures. UMEROUS investigators have described the tex- ture obtained by cold rolling the hexagonal metals, titanium, zirconium, and beryllium, which have c/a ratios less than that of ideal packing, 1.633. The basal planes are rotated out of the rolling plane, about the rolling direction, so that the basal poles are tilted toward the transverse direction as shown schematically in Fig. la. In all instances but one,' it was also reported that the [1010] direction was parallel to the rolling direction (see Fig. lb). Hot rolling has been reported as causing a similar tilt of the basal poles in the transverse direction (see Fig. la) and causing the [1010] direction also to be parallel to the rolling direction as shown schematically in Fig. lb. Annealing after deformation does not appreciably change the tilt of the basal poles in the transverse direction." Beryllium2-7 continues to have the [1010] direction in the rolling direction after annealing, and similar observations for titanium and zirconium' . have been reported for annealing at fairly low temperatures, again as in Fig. lb. At higher annealing temperatures, however, the recrystallized grains of titanium" and zirconium have an orientation such that the [1120] direction is approximately in the rolling direction, although the basal poles are still inclined in the transverse direction. Figs. la and lc show the resulting orientations schematically. This change in orientation has been described as a nominally ±30° rotation of the hexagonal crystallites about the basal poles of the cold rolled texture and is apparent from the results which are summarized in Table I for investigations with the X-ray diffraction technique employing film. The angles y, , and ß are indicated in Fig. 2 which represents the stereographic projection of (1070) poles for the mean orientation of a pole figure. Texture determinations for titanium using the Geiger counter spectrometer have provided similar results except that in some instances additional components of the texture were proposed, as shown by the summary of data in the upper half of Table 11. On the other hand, the spectrometer technique, when applied to zirconium,* has revealed a splitting Recently completed studies of the textures of annealed zirconium", show zirconium to possess textures very similar to those reported here for titanium. Therefore, much of this discussion will include zirconium by virtue of its close similarity to titanium in pref erred orientations. of the intense areas of the pole figure for samples annealed at 600°C. This splitting could be described by a 7" rotation of the tilt axis about the normal to the rolling plane. Such a splitting for the annealed texture relative to the cold rolled texture was not observed in other determinations for either zirconium or titanium using the less sensitive film X-ray methoe and makes the relationship between the two types of texture more complex than the simple rotation about the (0001) pole based on film work. The more precise investigations on zirconium permit the descriptions in the lower part of Table 11, which show that the texture depends quantitatively on the temperature of annealing. When zirconium is annealed at temperatures up to 400°C, the texture is similar to the cold rolled texture, while annealing in the range 500" to 900°C produces a texture which is only approximately described as [11%] in the rolling direction. More precisely described results for zirconium show that the two types of splitting ( 1—about an axis in the rolling plane through an angle given in the second column in Table II and 2—about the normal to the rolling plane through an angle given in the third column of Table 11) depend on annealing temperature. The [1120 is the rolling direction only when the annealing temperature is in the vicinity of 900°C

Jan 1, 1957

By C. J. Guntner, R. P. Reed

A commercial 18Cr-8Ni iron alloy (AISI 304L) was examined in tension at 300°, 76°, 20°, and 4°K. Continuous stress-strain recordings were made, X-ray analyses at periodic stress (strain) intervals were obtained, and the magnetic measurements were taken. From this data the percentage of martensitic products [bcc(a) and hcp (E)] was computed as a function of stress (strain). It was found thatup to 15 pct E phase forms at low temperntures. The amount of E formed increases to a maximum at about 5 pct strain, then decreases. This decrease indicates the additional transformation of E to a'. The total amount of E and a' was suppressed at constant stress (strain) at 4°K as compared to 76°K. It is proposed that the suppression of E and a' is associated with the decreased mobility of extended dislocations at very low temperatures. The yield strength decreased as the temperature was depressed below room temperature and then increased rapidly near 4°K. SOME ferrous alloys which are austenitic (fcc ?) at room temperature appear to be unique in that two martensitic products (hcp e and bcc a') may form on cooling to lower temperatures or on application of mechanical stress. The most common room-temperature austenitic ferrous alloys are 18Cr, 8Ni stainless steels. Most aspects of the spontaneous transformations have been previously described for these steels.' Several previous papers have described special aspects of the stress-induced transformations at low temperatures for the stainless steels, such as the existence of the hcp phase (c) after straining at 76oK,2-7 the morphology after straining using electron microscopy,7 and the decrease in E at higher strains at 76oK.4 However, for a complete representation, one must know the stress-strain characteristics and the dependence of both martensitic products on applied stress and temperature. It is the intention of this paper to provide that documentation. To accomplish this, continuous stress vs strain recordings were made at four temperatures: 300°, 76", 20°, and 4°K for annealed AISI 304L (a commercial 18Cr-8Ni alloy). At periodic stress intervals at each temperature the integrated X-ray line intensity of a selected peak for each phase (y, E, and a') was measured. In addition, photomicrographs of the strained surfaces were taken and magnetic measurements were made. The magnetic readings can be directly converted into percent a'.',e With these measurements the percentage of each phase may be plotted as a function of stress (or strain) and test temperature. It was found that up to 15 pct E phase forms upon stressing the AISI 304L alloy at low temperatures. The E percentage increases abruptly after the alloy yields, but then decreases gradually at higher stresses. The rapid increase in e at 76°K is associated with an "easy-glide" portion of the stress-strain curve. The total amount of a' + .G is suppressed below 76°K at a constant stress or strain. The yield strength decreases down to 76°K but increases rapidly below 20°K. EXPERIMENTAL PROCEDURE Tensile test specimens were cut parallel to the rolling direction from 0.1-in.-thick sheet. Continuous stress vs strain recordings were obtained at each test temperature (300°, 76o, 20°, and 4°K) using equipment and methods described elsewhere.' The specimens which were used in the X-ray analysis were stressed to successive increments of strain at each temperature, analyzed at room temperature, then restressed at the test temperature. This procedure was repeated until approximately ten X-ray analyses had been performed with approximately 1.0 pct strain increments. The specimens had a reduced section 1 in. long, 1.2 in. wide, and 0.1 in. thick. They were electro polished prior to testing and after each strain increment. Table I lists the chemical composition, grain size, and hardness for the alloy which was used. This is the same alloy for which extensive mechanical-property tests3 and morphological studies of the spontaneous transformations' have previously been made. For the low-temperature tests (76o and 4°K) below the Ms temperature the specimens were initially cooled to the test temperature, held for 1/2 hr, then warmed and X-rayed at room temperature. The results are listed in Table 11. From earlier work8 it was known that additional transformation on the second cycle would be considerably less (-0.1 pct

Jan 1, 1964

By R. E. Ogilvie, N. L. Peterson

Diffi-lsion measurements were conducted at all compositims in the bcc solid solution of the U-Nb system employing incremental couples at composition intemals of 10 at. pct. Diffusion coefficients were determined by the Matano method from concentration gradients obtained with the electron-probe microanalyzer. The activation energy for inter-diffi-lsion as a function of compositim shows three distinct regions: 1) 80 to 100 pct U.6= 30 kcal per mole; 2) 20 to 80 pct U, $ - 70 kcal per mole; 3) Oto 20 pet U, Q = i40 kcal per mole. The frequency factor, fi0 and the activation energy $ were found to be roughly related by the following equation: log Do ^9.7 X IO-5Q -6,6. The Kirkendall marker movement indicates that DU is larger than DNb between 16 and 100 pct U and DNb is larger than DU from 0 to 4 pct U. FOR practical as well as fundamental reasons, the rates of diffusion in alloys are of considerable consequence. Most solid-state reactions are largely dependent upon the diffusion of atoms through the lattice structure and along grain boundaries. The high-temperature strength and reasonable nuclear properties of niobium have prompted its use as a reactor material in contact with uranium fuel. Hence, diffusion data for the U-Nb system are of considerable importance. In the previous diffusion study1 on the U-Nb system using pure element couples, reliable data were obtained only in the range of 0 to 10 at. pct Nb due to the large variance of the diffusion coefficient with composition. Also, a large Kirkendall effect and considerable porosity in the uranium-rich areas of the specimen were reported, which suggests that the true diffusion coefficients are somewhat larger. The purpose of the present study was to obtain reliable diffusion coefficients at all compositions using incremental diffusion couples with intervals of 10 at. pct. In view of the abnormal self-diffusion be- havior of y uranium2-4 and some other bcc transition elements,&apos;-&apos; it was felt that a comparison of the interdiffusion coefficients in the bcc U-Nb system with those of Reynolds et al.9 for the fcc gold-nickel system might shed some light on the diffusion mechanism involved. Both systems have similar phase diagrams, in that complete solid solubility exists above a miscibility gap. EXPERIMENTAL PROCEDURE The uranium used in this investigation was obtained through the courtesy of Argonne National Laboratory. An analysis of this material detected only Si-30, A1-7, C-6, N < 10 and 0-18 ppm. The niobium was electron-beam melted material obtained from Stauffer-Temescal. The gaseous impurities were less than 50 ppm, and the spec troc hemical analysis showed Ta-500 and W-200 ppm. U-Nb alloys were prepared at composition intervals of 10 at. pct by melting the appropriate amounts of the pure elements in an arc furnace. The buttons were inverted and remelted 6 times to assure complete mixing. The buttons were then wrapped in molybdenum foil, canned in Zircaloy-2 or stainless steel, and hot rolled 30 pct reduction in thickness at temperatures between 850" and 1100°C. Alloys with 10, 20, 30, 40, and 90 at. pct Nb rolled quite easily under these conditions, but the 50, 60, 70, and 80 pct alloys remained brittle. After melting and rolling (when possible), the alloys were annealed for 24 hr at a temperature within 100°C of their melting point in a dynamic vacuum of better than 4 x 10-8 mm Hg. These treatments produced alloys which were homogeneous on a 1 p scale within the detectability limits of the electron probe. During fabrication, the alloys picked up as much as 100 ppm Mo and 100 ppm Zr. Other elements checked for but not found were Co, Cr, Fe, Mn, Ni, and Ti. The grain size of the annealed samples ranged from 3 mm for the uranium-rich alloys to 0.3 mm for the niobium-rich alloys. This permitted measurements of the concentration gradients in the diffusion samples without crossing more than one or two grains, thereby eliminating any grain boundary effects. The specimens were bonded by theU&apos;picture frame" technique as reported by Kittel.10 Specimens of composition b)U + (100 - x)Nb were sandwiched between two specimens of composition (x + 10)U + (90 - x)Nb after they were ground flat and parallel

Jan 1, 1963

By Forrest V. Williams

The dislocatiorl and stacking-fault structuve of epitaxial GaAs1-,PX lms been examined by chemical etching. The layers were groun in the (100) direction and etch Pils were developed on (111} planes which nad been lapped and polished on the epiLaxia1 layevs. Tile effecL of the jollolcing cariables on the quality of the epilaxial layers has been examined: doping leuel, grouth rate, and composition. High stacking-faullL densilies weve found in the GuAsi_xpx layers. These are not observed in heavily dolled epitaxial layers tzar in layers with low phosphorus compositions. The dislocatiorz density in GuAsi-x px was highest at the sub-stvate- epilaxia1 layer interface. Composilion changes introduced dislocations in the epitaxial layers. ManY semiconductor p-n junction lasers of Group TIT-Group V compounds and their alloys have been reported in the past several years. Laser action at visible wavelengths in GaAsl-x,Px was first reported by Holonyak and Bevacqua. GaAs, a direct transition semiconductor which lases, and Gap, an indirect transition semiconductor which does not lase, form a continuous series of solid solutions.2 Laser junctions can be fabricated in GaAsl-xPx crystals with phosphorus compositions up to about 40 mol pct. In addition to the production of coherent radiation in these crystals, the efficient recombination radiation of p-n junctions in this material has equally important potential in the development of low-power semiconductor lamps. To achieve a high conversion efficiency of electrical to optical energy in p-n junctions in this material, the relation of physical properties of the crystal to luminescence efficiency must be better understood. Although the electrical, optical, and device properties of GaAsl -xPx junction lasers are understandably of considerable interest, the work to date indicates that the more serious problems are the chemical and metallurgical difficulties encountered in the growth of this material.3 In addition to the problems of chemical purity, crystal imperfections, such as dislocations and stacking faults, can be expected to affect both the efficiency of the radiative recombination process and the perfection of the p-n junction.3 The last requirement, i.c., that of the perfection of the p-n junction, is a particularly troublesome one in the fabrication of laser diodes. To obtain good laser diodes, the p-n junction must be flat, which permits the radiation to be reflected from the resonant cavity boundaries. Junction planarity is extremely sensitive to the crystal perfection of the semiconductor material. Also, it is known that at high dislocation densities (-105 per sq cm) it has not been possible to build laser junctions in GaAsl-xPx . Few studies have been reported on the crystal defect structure of GaAsl-,P,. The first serious study seems to be that of Wolfe, Nuese, and Holonyak,3 who examined the dislocation structure of monocrystalline bulk (nonepitaxial) material grown by halogen vapor transport. In this paper are reported some observations on the dislocation and stacking-fault structure of GaAsl_,P, crystals grown by a vapor transport process on substrates of GaAs. EXPERIMENTAL Crystal Growth. The GaAsl-xPx crystals were grown in an open-tube flow system, using two sets of reagents. GaAs, Pr(red), and HC1 were employed in one method. The transport reaction is =950JC GaAs+HC1 = GaCl +1/4As4 +1/2H2 and the deposition reaction is 2GaAs1-xPx +GaCl3 Composition control is obtained by the flow rate of the HC1 and the vapor pressure of the P4, which is maintained in a separately controlled furnace. The second method has been described by Ruehr-wein4 and utilizes gallium, AsH3, PH3, and HC1. The same transport and deposition reactions as above are involved. Composition control is obtained solely by the flow rates of the three gases involved. All of the crystals were grown on chemically polished GaAs substrates oriented on the (100) plane. The thicknesses of the epitaxial layers were typically 100 to 300p. Revealing of Dislocations. Dislocations were re-vealed on both the( 111 ) and { l l l }b faces by chemical etching. The specimen to be examined was mounted at 54.7 deg, lapped on glass with 3-p alumina, polished on cloth with 3-p diamond paste, and, to remove work damage, chemically polished at room temperature for

Jan 1, 1968

By Tilden Cummings

The extractive mineral industries share a number of common characteristics and basic problems which are completely different from those associated with manufacturing and mercantile operations. These industries now supply about 95% of the inanimate energy consumed in this country, and share with agriculture in providing virtually all of our basic raw materials. Mineral producers, like farmers, are subject to the economic hazards of fluctuating markets and prices. Unlike farmers, however, they cannot renew the productivity of the earth, but must seek continually for new sources of supply. The necessity for exploration and development of new reserves, to replace those used up by production, introduces additional factors of economic risk. These operations require the expenditure of large amounts of capital, often well in advance of any assurance of profitability. Commercial banks that understand these special problems can provide a variety of constructive financial services to the mineral industries. The history of cooperation between banks and mining enterprises has yet to be written, but there is every indication that it would encompass a period of hundreds of years. Records refer to depository and lending services by the early European private bankers involving precious metals and jewels. Many of the exploratory voyages to the Far East and the New World were organized with the financial backing of wealthy syndicates, some of which also provided banking services, in the hope of finding new sources of gold and other precious minerals. In the United States many large banks are closely identified with the development of some of the larger mineral deposits such as the Mesabi Range and the gold fields of California.

Jan 5, 1965

By K. G. Davis

Dilute alloys of silver and of thallium in tin have been solidijzed unidirectionally under controlled conditions, to study the segregation associated with a cellular interface under conditions where both thermal and solute convection are present. Autoradiography and radioactive tracer counting techniques were combined with electron-probe microanalysis to study both macro- and microsegregation. It was found that, for concentrations giving only small amounts of constitutional supercooling, cell formation had little effect on the macroscopic distribution of solute along the specimen. At higher concentrations the effective distribution coefficient was higher than that expected for a smooth interface. Node spacing was independent of initial solute content at lower concentrations, becoming greater as keff increased. Silver content at the segregation nodes of silver in tin alloys was independent of initial concentration and considerably in excess of the eutectic composition. SINCE the investigation of cell formation at advancing solid-liquid interfaces by Rutter and Chalmers,&apos; a large volume of work has been dedicated to the determination of solidification conditions under which a planar interface will break down into cellular form. Early experiments were explained satisfactorily by the concept of constitutional supercooling,2 but, due to poor measurement of temperature gradients in the liquid, lack of accurate data on liquid diffusion and equilibrium distribution coefficients, and uncertainty about the effects of thermal and solute convection, these experiments cannot be used as proof for the theory. More recent work, however, has shown that under conditions where convection is eliminated or can be ignored good correlation is observed.3,4 Investigations into segregation at cell caps5 and at cell nodes6-&apos;&apos; have been made, but no measurements appear to have been done on the overall, macroscopic segregation down a unidirectionally solidified rod of material which has solidified with a cellular substructure. This has practical importance in casting, where regions of material with cellular substructure are often encountered, and also in zone refining where the thermal conditions necessary for a planar interface are unattainable. Further, as will be shown, the macroscopic segregation can give information on the following question. Granted that a cellular solid-liquid interface develops from a planar one when the conditions for constitutional supercooling are exceeded, how much supercooling is present after the cells have formed? EXPERIMENTAL PROCEDURE AND RESULTS Specimen Preparation. Specimens 25 cm long with a square cross section 0.6 by 0.6 cm were grown in graphite boats by solidification from one end. Alloy compositions are given in Table I. Two specimens of each composition were grown. The tin was 5-9 grade and the silver and thallium both 4-9 grade. Ag110 and Tl204 were used as tracers. Each composition had the same quantity of tracer so that auto radiographs of specimens containing different concentrations of the same element could be easily compared. Thermocouples inserted through the lid of the boat into a dummy specimen showed that, over the first 10 cm of growth, thermal conditions were quite steady, with a rate of interface advance of 5.8 cm per hr and a temperature gradient in the melt ahead of the interface of 3.0°C per cm. The specimens were seeded from tin crystals of a common orientation to eliminate orientation effects. Dilution of the specimen by seed material was minimized by the provision of a narrow neck between specimen and seed crystal. Macrosegregation. After growth, the specimens were sectioned with a spark cutter. The rods of silver alloy were cut into 1-cm lengths and analyzed for Ag110 using a y -ray counter with fixed geometry. The specimens containing thallium were cut into 2-cm lengths and analyzed for T1 204 by taking 13 counts from each end of the cut lengths through an aperture in lead sheet approximately 0.4 cm square. The results are summarized in Figs. 1 and 2. To find the effective distribution coefficient for the silver in tin alloys under smooth interface conditions, the region of substructure at the bottom surface of one of the 10 ppm specimens, see Fig. 3, was removed by spark machining before counting. Autoradiography. For both alloy systems the samples were polished on sections taken alternately parallel and perpendicular to the growth direction, and autoradiographed by placing the polished surfaces in contact with Kodak "Process Ortho" film. Figs. 3 and 4 show the structures revealed. The alloy containing 10 ppm Ag showed substructure only after a few centimeters of growth, and then substructure was limited to a narrow layer at the base. The "speckled" substructure reported previously in this system4 is here clearly seen to be an intermediate stage between planar and cellular interface conditions. The other samples show a remarkable similarity considering

Jan 1, 1969

By C. G. Dunn, J. L. Walter

Secondary recrystallization to the (110) [001] texture in high-purity silicon iron occurs if low-oxygen material is annealed in a nonoxidizing atmosphere. Any departure from these conditions results in a growth of (100) oriented grains. The nature of the matrix and secondary recrystallization structures and textures and the nature of grain boundary interactions during growth show that the low gas-metal interfacial energy of the (110) surfaces provides the driving force for growth of these grains. A type of grain growth, characterized by a driving force which derives from energy differences of {hkl} surfaces at the gas-metal interface, has been treated in recent papers.&apos;-7 Secondary recrystallization to the cube text!:: in high-purity silicon iron provides one example. The present paper also deals with a surface energy driving force but the texture that results by secondary recrystallization is not the cube texture; it is a texture in which the (110) plane is in the plane of rolling and the [001] direction is in the direction of rolling. The phenomenon described in this paper is different from the impurity (dispersed phase)-controlled secondary recrystallization process in which the (110) [001] oriented grains grow under the action of grain boundary driving forces.8-12 It is also different from tertiary recrystallization,2 which also produces the (110) [001] texture in high-purity silicon iron, since the matrix textures and grain sizes are different. Finally, it is unlike any other form of secondary recrystallization reported in the literature. The possibility of obtaining the (110) [001] texture in high-purity silicon iron became clear in a study of the effect of impurity atoms on the energy relationships of (100) and (110) surfaces. In this study Walter and Dunn6 observed the migration of (100)/(110) boundaries, i.e., boundaries between two grains, one of which has a (100) plane and the other a (110) plane, respectively, parallel to the plane of the sheet specimen. At 1200°C the (100)/(110) boundaries advanced into (100) grains in a vacuum anneal, then reversed their direction and migrated into (110) grains in a subsequent anneal in impure argon. Finally, the direction of migration reversed once again with (110) grains growing into (100) grains in a second vacuum anneal. These results were explained in terms of a change in concentration of oxygen atoms at the gas-metal interface during the anneals. Thus, oxygen atoms were added to the surface during the anneals in impure argon to the point where ?100, the specific surface energy of the (100) oriented grains, was lower than ?110, the surface energy of (110) oriented grains. In vacuum, however, the oxygen concentration at the surface was lowered to the point where ?110 < ?100. Concerning the possibility of secondary recrystallization in high-purity silicon iron with a low initial oxygen concentration, the observed effect of adsorbed oxygen atoms has indicated6 that a good vacuum anneal would favor the rapid growth of matrix grains with the (110) plane in the plane of the sheet much more than grains in the (100) orientation. The growth of only (110) oriented grains of course would depend upon y110 being less than ?hkl, where hkl refers to any plane different from (110). The present paper is concerned with the application of the above ideas to secondary recrystallization to the (110) [001] texture in high-purity silicon iron. The matrix and secondary recrystallization textures and structures are defined and discussed. Observations of growth of nuclei for secondary recrystallization and of boundary interactions are included to provide direct information on the surface energy relationships between (110) and other (hkl) surfaces. EXPERIMENTAL PROCEDURE As before, 2,4-6 high-purity iron and silicon were melted and cast in vacuum to provide an alloy containing 3 pct Si with less than 0.005 wt pct impurities. The oxygen content of the ingot was lower than in previous ingots, being approximately 3 ppm (by weight). The carbon content of this ingot may have been slightly higher than was found for previous ingots. The same rolling and annealing schedule used previously2 was followed in this study to obtain samples 0.012 in. (0.3 mm) thick. These samples were electropolished prior to annealing. After rolling and polishing, the oxygen content of the material was approximately 6 ppm; material used in the previous studies contained about twice this amount of oxygen.

Jan 1, 1961

By Milton Lissberger

MILTON L. LISSBERGER, ? New York, N. Y.-Solder is a mechanical mixture of tin and lead, a fact which is susceptible of very simple demonstration. A bar of solder of a grade even as low as 30 per cent. tin and 70 per cent. lead, passed through a buffing machine, will show a surface practically identical with that of a bar of second-quality or reclaimed tin. The buffings, on chemical analysis, will prove to be almost pure lead. According to the best practice, solder is made in the following manner. Virgin pig lead is first melted, and when it is thoroughly liquefied, virgin pig tin is added, together with a small amount of flux; the latter is for the purpose of bringing to the surface the so-called "liver," consisting of impurities that may have remained in either the lead or the tin as a result of incomplete refining. The combined material, when completely liquid, is thoroughly stirred for some hours, and is then cast into small pigs. Just before casting, and continuously during this operation, the molten metal yields dross, consisting largely of the oxides of lead and tin; this should be carefully skimmed off. After the pigs have cooled, they are taken to a smaller kettle, remelted, and cast into the desired shape for use; or if wires, ribbons, etc., are to be made, the solder is cast into slugs suitable for extrusion and rolling. During this second operation, the skimming of dross should be even more carefully done than at first. Hand mixing has proved to be the only reliable method for the production of the best quality of solder, irrespective of its percentages of lead and tin. The best quality of solder is not necessarily that which contains the highest percentage of tin, but rather is that composition which performs best on the required piece of work. In order to produce

Jan 12, 1918

By Walter Wood

The specifications for cast-iron pipe that have been submitted at this meeting are practically the outgrowth of those which were originally adopted, about 1860, by Mr. Kirkwood of Brooklyn, N. Y. They have been changed but little since that time, the mode of testing pipe in the hydraulic press, as well as the method of coating, not having departed from the original practice. The chief addition to the specifications has been in the adoption of a test-bar 2 in. by 1 in. in crosa-section, broken between 24-in. supports by a transverse strain applied on the flat side. Test-bars were first introduced into pipe-specifications about 1870. At that time a satisfactory test-piece had to stand a tensile strain of 16,000 lb. per square inch. The present test-bar was adopted in order to give some idea of the deflection of the iron that was being used. These deflection-tests have been so satisfactory to both engineers and manufacturers, and have met the requirements of the pipe-trade so accurately, that it is considered best to hold to the . 2-in. by 1-in. bar instead of adopting the short " Arbitration Bar," which yields but little information from the stand-point of deflection. The new feature in these specifications is the effort to reach standards to which pipe shall be cast in the future, thus permitting the manufacturer to make up stock and the purchaser to find material on hand when he asks for deliveries. Heretofore there has never been ally standard weight for pipes? although in some sizes certain weights are more frequently asked for than others. The fixing of standards for pipes permits the adoption of definite standards for fittings. It has been aimed to secure such uniformity for fittings as will permit the same class of fittings to cover two or more classes of pipe. In order to accomplish

Jan 1, 1905

By H. M. Chance

WITHIN the last 10 years the subject of mine taxation in its relation to coal-mining interests has come to have growing importance, not only to those engaged in the mining of coal, but also to the owners of land underlain by coal. A disposition has developed among legislators to accept the principle, which has been laid down y many judicial decisions, that coal underlying the surface must be regarded as a part of the real value of all properties so underlain, and as such is chargeable with such burdens of taxation as the necessities of the government may impose. These necessities arise from the normal expense of maintaining State and local governments, and in the past have been met principally by, taxes based upon assessments of real estate values, which values in many cases have been confined principally or wholly to the value of the surface, without taking into consideration the value of minerals underlying the surface. It is not proposed here to deal with the question of Federal taxation, whether levied on production, or on products transported from one State to another, or exported from the country, or upon thegross or net earnings of corporations engaged in interstate commerce, or upon the production of materials which may be transported from one State to another, or levied. upon the profits or upon the obligations of corporations. The present discussion will be confined to the appraisal of coal lands as assessed for State, county, township, or borough taxation. The methods heretofore and at present in use in the different States vary widely and have resulted in more or less litigation. Discussions appearing from time to time in the technical and trade journals and in the proceedings of mining and engineering associations frequently direct attention to the need for the adoption of fixed principle in levying taxes, and of uniform methods for applying such principles, but there does not seem to be a general demand from the public for the adoption of such methods.

Jan 7, 1914

By G. H. Bishop

The kinetics of the inter granular penetration and embrittlement of [100] tilt boundaries in 99.998 pct pure nickel upon exposure to bismuth-rich Ni-Bi liquids have been determined in the temperature range from 700° to 900°C. The kinetics of penetration are parabolic in time at constant temperature over most of the temperature range. In a series of 43-deg bicrystals the rate of penetration is anisotropic with respect to the direction of penetration into the grain boundaries. In lower-angle bicrystals the penetration rate is isotropic. The rate of penetration decreases with tilt angle at 700°C. The activation energy for penetration in the 43-deg bicrystals is 42 kcal per g-atom independent of direction. It is concluded that the intergranular penetration and embrittlement in the presence of the liquid proceeds by a grain boundary diffusion process and not by the intrusion of a liquid film. This was confirmed by a determination that the kinetics of penetration and embrittlement were the same in the 43-deg bicrystals upon exposure to bismuth vapor under conditions such that no bulk liquid phase would be thermodynamically stable. WhEN solid metals are exposed to a corrosive liquid-metal environment, the grain boundaries are sites of preferential attack. Depending on the temperature, the composition of the liquid, and the composition, structure, and state of stress of the solid, a number of modes of attack are possible. This paper reports a study of the kinetics of intergranular penetration and embrittlement of high-purity nickel bicrystals upon exposure to bismuth which, together with an earlier study by Cheney, Hochgraf, and Spencer,&apos; demonstrates that there are at least two modes of intergranular attack possible in the Ni-Bi system. In the study by Cheney et al., columnar-grain specimens of 99.5 pct pure nickel were exposed to liquid bismuth presaturated with nickel in the temperature range 670" to 1050°C. They found that the majority of the boundaries, which were predominantely high-angle boundaries, were penetrated by capillary liquid films, the attack proceeding by a process which will be termed grain boundary wetting. This process occurs in a stress-free solid when twice the liquid-solid surface tension is less than the surface tension of the grain boundary,* i.e., when 2yLs < YGB In this case the penetration of the grain boundary by the liquid occurs at a relatively rapid rate, resulting in the severe embrittlement of a polycrystalline solid. Grain boundary wetting is a common mode of intergranular attack in systems in which the lower melting component is relatively insoluble in the solid, but the solid has an appreciable solubility in the liquid, for example, the Ni-Bi system, Fig. 1. In systems of this type at temperatures above the range of stability of any intermetallic phases, once the liquid is saturated with respect to the solid so that no gross solution occurs, chemical gradients are small, and surface tensions become major driving forces for attack, provided the solid is stress-free. The results of Cheney et al. appear to be typical of those encountered when grain boundary wetting occurs.&apos; Capillary films were observed in the boundaries after quenching from the exposure temperature. The mean depth of penetration increased linearly with time, and the activation energy for the process was found to be 22 kcal per g-atom. In a study of the Cu-Bi system Yukawa and sinott4 found that the depth of penetration of bismuth into high-purity copper bicrystals of orientations from 22 to 63 deg of tilt about (100) at 649°C ranged from 0.05 to 0.25 in. after a 12-hr anneal. This corresponds to a linear rate of 6 to 15 X 10~6 cm per sec. At the same reduced temperature of 0.68 the rate for the Ni-Bi system&apos; was 7 x lo-&apos; cm per sec. In another study of the Cu-Bi system, Scheil and schess15 determined the kinetics of grain boundary wetting in hot-worked commercial rod. While there were several complicating factors present in this study, there is general agreement with the above results. The kinetics of penetration were linear, the activation energy was 20 kcal per g-atom, and at 650°C the rate of wetting was 2 to 5 x 10-6 cm per sec. The rate of wetting in the A1-Ga system6 is somewhat

Jan 1, 1969

By W. B. Heroy

ONLY through the mineral fuels can large amounts of energy be transported to great dlstances and stored for long periods for future use. Coal has the advantages over oil of greater safety of handling and smaller losses in storage. But oil is, in the present stage of technical advancement, the more economical source of liquid fuel for internal-combustion motors. No method for direct use of coal in such motors has been developed that can compete with petroleum products. The automoblle engine and the airplane motor are designed to make the most effective use of gasoline.

Jan 1, 1944

By Jose M. Sobral

The approximate production of petroleum in the various fields and for the country as a whole is shown in the following table, the figures for the later months of the year being estimated. Among the developments of the year may be mentioned the finding by the Standard Oil Co. of a small production, about 6290 bbl., at Aguas Blancas in the Province of Salta near the Bolivian border, and of about 88,000 bbl. at Lomitas, near Tartagal in the same province. The Government (Yaciementos Petroliferos Fiscales) in the last four months of the year also obtained about 6290 bbl, from Quebrada Galarce. .The oil found in Salta is of good grade and while the quantity is small great hopes of larger production are entertained. Approximate Total Argentine Production for 1928 Barrels Barrels Comodoro Rivadavia............................... 8,165,615 Plaza Huincul..................................... 783,514 8,949,129 Distribution of Production Government, Comodoro Rivadavia................... 5,165,159 Government, Plaza Huincul......................... 306,166 5,471,325 Private, Comodoro Rivadavia....................... 3,000,456" Private, Plaza Huincul............................. 477,348b 3,477,804 a The companies represented are Astra, 649,474 bbl.; Oriente, 42,237; Ferrocar-rilera, 1,337,380; Comp. Indust. y Comm., 609,092, Solano, 64,158; Diadema, 298,114. b Standard Oil Co. and a few smaller companies, Exploratory drilling has also been conducted around the Comodoro Rivadavia field. The Government is drilling at Vuela del Senguer south of Colonia Sarmiento and about 200 km. west of the main field hut the prospect of success is not as yet large. The country around Castillo, where the Royal Dutch Co. has property, is regarded more favorably. perhaps the most interesting event of the year was the discovery of a productive horizon at Comodoro Rivadavia about 200 m. below that previously exploited. This new horizon was found by the Ferrocarrilera Co. at 769 m. in its well No. 81, the previous yield for this

Jan 1, 1929

E. W. Parker, Washington, D. C.: In connection with Mr. Blauvelt&apos;s paper, a brief sketch of the development of by-product coke-making in the United States may prove of interest. The first radical departure from the prevalent beehive oven to the by-product retort oven was inaugurated in 1891 by the Solvay Process Company, at Syracuse, N. Y. In that year was begun the construction of 12 Semet-Solvay ovens, which were completed in 1893. During 1893 these ovens produced 12,850 tons of coke, an average.of a little over 1000 tons each. In the following year the production amounted to 16,500 tons, not quite 1400 tons per oven. These 12 ovens were in reality an experiment, the success of which was attested by the addition to the same plant of 13 more ovens, begun in 1895 and completed in 1896. They were followed by the construction in 1896 of 25 ovens of the same type at Sharon, Pa., and 50 more at Dunbar, Pa. These 100 ovens represented the total number of Semet-Solvay ovens completed and in operation up to the close of 1897. The construction of 180 more, however—120 at Ensley, Ala., and 60 at Benwood, near Wheeling, W. Va.—was begun in 1897. The plant for the latter is laid out for double the number stated. The 60 ovens begun in 1897 have now been completed. An initial plant of Otto-Hoffman ovens was built at Johnstown, Pa., in 1895, and began making coke in 1896. One hundred and twenty additional ovens of this type were begun in 1896 and completed in 1897 at Glassport, near McKeesport, Pa. During the present year 100 Otto-Hoffman ovens are being added to the plant at Johnstown, and 400 of the same type are in course of construction at Everett, near Boston, Mass. The plant at the latter place is laid out for a total of 1200 ovens.

Jan 1, 1899

Discussion of the paper Of ROBERT H. BEDFORD and WILLIAM HAGUE, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin No. 92, August, 1914, pp. 1807 to 1816. W. L. SAUNDERS, New York, N. Y. (communication to the Secretary *) . -Messrs. Bedford and Hague have given us a very interesting and practical paper. No better excuse for such a paper could be desired than the statement made that the expense of drilling. in this mine is one-third of the cost of delivering the ore at the mill. This statement. should be written in red letters, because it applies to a great many mines besides the one referred to and because it is generally true that in a mining plant, as also in papers read before the Institute, more attention by fat is given to the metallurgical side of mining than to the excavation of the ore, and no study of the excavation work is properly made that does not involve a careful inquiry into the merits of the rock drill used. Next in importance to the selection of a good rock drill, in a case where the actual drilling cost is one-third the cost of delivering the ore, is that. the drill should be maintained in order and kept up to its highest efficiency. The best rock chill may run down in efficiency through accidents, wear, or other conditions which are sometimes beyond supervision or control. The machine is usually in the hands of men who know how to get workout of it, not men who know how it works. The best drill runners are not machinists,. but miners. They could not tell you how the valve operates or the principle of the rotation, but they know how to get the work done. A testing machine, particularly the type described in this paper, may he of the greatest value in maintaining a uniform state of efficiency.

Jan 11, 1914

By Jacob T. Wainwright

AS a means for increasing the efficiency in modern blast-furnaces by supplying to them blast of a much higher temperature than is now possible, the writer offers as a suggestion a modification in the construction of regenerative hot-blast stoves. Stated briefly, the plan proposed is to pre-heat both the gas and the air for its combustion in a manner similar to that generally adopted in Siemens openhearth furnaces. After thus carrying the temperature of the stove to a point much higher than that common in hot-hlast stoves, the cold blast passes through it. Without entering into the details relating to the reversing valves and the system of flues, the general plan may be outlined as follows, referring to the accompanying drawings: The valves are so placed in heating up the stove that the blast-furnace gas enters at B, Fig. 1, and the cold air for combustion at A. Ascending in flues, F and E, respectively, combustible gas and air meet and mix in the combustion-chamber, I. Flowing through K, they descend through the flues, G and H, escaping through the chimney. In this manner the walls of the combustion. chambers, I and L, are highly heated, and the right-hand side of the stove is carried to a higher temperature. By reversing the valves, blast-furnace gas enters at C and cold air for combustion at D. Both are pre-heated in their ascent through the flues, G and H. They burn in the combustion-chamber, L, and the hot gases of combustion, flowing through K, I, E and F to A and B, heat the left-hand side of the stove. In this manner the stove is carried to a temperature greater than that of those now generally in use, in which air and gas are burned without preliminary pre-heating. In the plan proposed, that side of the stove will, of course, be relatively cooler through which cold air and furnace-gas last passed in its ascent to its combustion-chamber. After having sufficiently heated the stove in the manner outlined, the cold blast is admitted through all the flues, A, B, C and D. It ascends through the highly-heated regenerative material to the chambers at the top and descends through the flue, P, Fig. 2 (dotted

Jan 1, 1889

By Ralph Wilcox

The diamond drilling of certain characters of unstable rock formation, as, for example, the copper-bearing schists of the Miami district in Arizona, is rendered most difficult by what is known as a caving " of the sides of the drill holes. As this caving is very greatly increased by the action of flowing water, it occurred to me, after experiencing a great deal of difficulty with caving in diamond-drill holes which I was drilling for the Miami Copper Co., that if I could substitute air for water, much of the caving—with resultant difficulties, such as decreased speed of sinking and increased consumption of diamonds—would be overcome. After some experimenting, I found that it was perfectly practicable to substitute air for the water; forcing the air down the hollow rotating rods in the same manner as is done with water, the air passing out around the bit, which is thus cooled, and ascending on the out~ide of the rods to the collar of the hole, carrying the borings in just as satisfactory a manner as had been done by the water, but without the accompanying destruction or caving of the sides of the drill holes such as had been so generally experienced with the water. When water was encountered in the drilling this water was forced up to the collar just as it would have been had water been used in the drilling, but with the correspondingly decreased flow there was relatively less washing or caving of the sides of the drill holes. The only change necessary in the arrangement of the drill is that a cross instead of a tee is used at the collar of the hole. A tightly woven jute bag is attached to one arm of the cross, for collecting and filtering the sample; and when drilling in dry ground a jet of water is attached to the opposite arm of the cross, to collect the dust and wash down the sample into the bag. The rods rotate through a stuffing box attached to the upper opening of the cross. The distention of the jute bag by the issuing air indicates the operating conditions as sufficiently as did the flow of water when using water in the drill hole. The small percentage of core recovery rendered it necessary to

Jan 1, 1914