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By L. R. Weisberg, E. A. Miller

Single-crystalline films of silicon of good quality were vacuum-deposited on sapphire. The improved crystallinity was achieved by the strict exclusion of oxygen from the evaporation system, including the use of a "oxygen-free" silicon source. To minimize possible contamination of the source, the silicon was sublimed from the solid at about 1390° C. using a simple electron bombardment system to heat the silicon. This resulted in deposition rates of about 5 to 7 µ per hr and film thicknesses of 4 to 20 µ. The vacuum during deposition was ordinarily about 5x 10-8 Torr, DESPITE the success achieved in the chemical vapor deposition of silicon on sapphire using Silane,1-4 vacuum deposition has not provided comparable properties. For example, Chu et a1.5 vacuum-deposited silicon on single-crystalline substrates of A12O3, Sic, ThO2, and other compounds, and, although some epi- but the use of ultrahigh vacuum (about 1 to 3 x10-9 Torr) during deposition did not significantly improve the results in the oxygen-free system. The crystalline quality of films deposited on (0001) sapphire was found to be considerably superior to (1102) sapphire surfaces. Using (0001) sapphire, single-crystalline films were deposited at temperatures as low as 780° C and as high as 1075°C, with the best crystalline quality obtained at about 1000°C. At this temperature, hole mobilities over 250 sq cm per v-sec were achieved. taxy was indicated, single-crystalline films were not produced. More recently, Salama, Tucker, and young6 evaporated silicon on single-crystalline sapphire, but only poor crystallinity was observed, and low carrier mobilities were measured. In the present experiments, good-quality single-crystalline films of silicon on sapphire have been achieved by specifically excluding oxygen from the evaporation. This included not only the use of a "clean" vacuum system but, of special importance, the use of an oxygen-free silicon source. This has also been shown to provide a dramatic improvement in silicon homoepi-taxy.7 As a result, silicon-on-sapphire films with hole mobilities over 250 sq cm per v-set were achieved, and single-crystal films were grown as low as 780°C and as

Jan 1, 1969

By J. J. Kramer, K. Foster

The orientation distribution of surface-energy -induced secondary recrystallized grains was determined. This work was conducted on thin sheets of a 3 pct Si-Fe alloy annealed under environmental conditions that furor grouth of grains with a (100) plane in the surface of the sheet. The texture was found to be extremely sharp and almost independent of sheet thickness. The distribution varied exponentially with the angular deviation from the {100} plane. It was possible to relate the distribution to the nu-cleation rate of the secondary rains as influenced by the surface-energy difference. THE role of surface energy in the secondary grain growth of cube-oriented grains (grains with a (100) plane in the plane of the sheet) in thin Si-Fe sheets has been previously discussed.1-4 In high-purity sheet material normal grain growth usually occurs until the grains have extended through the sheet. Further grain growth is inhibited by the thermal grooving of the boundaries at the sheet surface. However, additional growth of cube grains can occur by a secondary grain growth process under conditions where the (100) plane has a lower surface energy than other orientations. Apparently for these alloys, cusps exist in the polar plot5 of surface free energy with the lowest cusp energy occurring at the (100) orientations. This has been reported to be the result of preferential adsorption of sulfur on the (100) planes.6 As a result of this process, a distribution of orientations could arise from two possible mechanisms. First, when a cusp is present in the polar plot of surface free energy, there are orientations inside the cusp that have a lower surface energy than elsewhere on the polar plot. Also, at sufficiently high temperatures, flat surfaces whose orientations are inside or just outside the cusp (depending on its shape) can often thermally etch, yielding a microscopically stepped surface of even lower surface energy. As a result, grains oriented close to cube would also have a lower surface free energy, either because of the cusp shape or by thermal etching, and could possibly grow as secondary grains by the surface-energy phenomenon. One should thus observe a distribution in the surface orientation of the cube grains comprising the secondary structure. It is the purpose of this paper to investigate this orientation distribution experimentally and to discuss the factors involved in its formation. For this purpose, the surface orientations of a large number of secondary grains in various sheet thickness were determined by means of the Laue back-reflection X-ray technique. PROCEDURE A vacuum-melted 3 pct Si-Fe alloy containing a nominal impurity content of 0.005 wt pct was processed into strip. A single cold-rolling step of 90 pct reduction was used for each strip regardless of the final sheet thickness. Final strip thicknesses of 0.60, 0.30, 0.15, and 0.075 mm were used. Care was taken to insure that the final strip surface was smooth and flat. All strips of a given thickness were annealed together at 1200°C in dry hydrogen (dew point -70°C) to develop the desired secondary structure and to insure identical environmental annealing conditions. The annealing time was selected to develop a complete secondary structure in the thinner sheets but to permit the thicker sheets (0.60 mm) to have residual primary grains remaining. This was necessary to determine whether growth impingement could lead to one secondary grain consuming another at a greater angular deviation. For the X-ray determination of the surface orientation of the secondary grains, a special specimen holder was used. The camera and holder arrangement could be aligned by X-raying a grain in three positions rotated 180 deg to each other. Thus, with a small beam X-ray focus (1 mm), the surface orientation of any grain could be determined to within one-half a degree. The surface orientations of one hundred cube secondary grains were determined for each sheet thickness. The criteria of a secondary grain were its size relative to the sheet thickness and the number of sides of the grain observed in the sheet surface. (A primary recrystallized grain extending through a sheet will generally have six edges visible in the plane of the sheet, whereas a secondary grain will have many more when growing entirely into primary grains.) Grains were selected as randomly as possible by X-raying every secondary grain found along a line drawn on the strip. No attempt was made to determine the exact orientation of the planes of the surface, as many strips from randomly selected sheets were used. On1y the angular deviation of the surface plane from {100} was measured. In order to assess the volume distribution in the

Jan 1, 1965

By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half'-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.'' The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By R. W. Smith

There are many inconsistencies and gaps in available information concerning the mechanism whereby dodecylamine acts as a collector for quartz. The author compares the studies which have been made in correlating the contact angle with adsorption density on quartz over all pH ranges, and attempts to resolve some of the inconsistencies. In recent years much information has been obtained concerning the mechanism whereby dodecylamine acts as a collector for quartz. Fuerstenau,1 for ex- ample, has shown that adsorption density and zeta potential under some conditions, at least, can be correlated with contact angle and flotation rate. There appear, however, to be several inconsistencies and gaps in information available. One inconsistency involves trying to correlate contact angle with adsorption density on quartz over all pH ranges. Fuerstenau's correlation at a collector concentration of 4x10-5 moles per liter dodecylamine acetate and about pH 10 shows a contact angle of about 80 degrees occurring at approximately monolayer coverage. If Gaudin and Morrow's2 and Morrow's3 contact angle data for near neutrality (pH 6 to 7) are now compared with deBruyn's4,5 adsorption data on quartz in a similar pH range, it will be noticed that a contact angle of 38 to 40 degrees corresponds to complete monolayer coverage (at an amine concentration of approximately 10"3 molar). In fact even at an amine

Jan 1, 1963

By J. R. Finlay

BEFORE entering into the statistical part of this article, some general comments may be ln order. Each important war seems to introduce a new atmosphere and a new epoch. The Civil War led to the period of great interior development in North America, of the transcontinental railroads, and of large-scale manufactures. The first World War introduced the general use of the automobile, the building of a huge network of highways, the radio, and household engineering. Now I expect World War II also to introduce some new ways of living. Transocean aviation will become a commonplace; we shall probably have much more of an eye to our military and naval establishments and be more conscious of Eastern Hemisphere affairs instead of thinking so exclusively of the Western. Each war has also multiplied government expenditures and taxes; and to this rule the present one will certainly be no exception.

Jan 1, 1944

By N. J. Grant, B. C. Giessen, R. Koch

The system Nh-Ir was investigated over the complete concentration range by metallography and X-my techniques, using forty one alloys. The solubility limits of terminal and intermediate phases and the solidus temperatures were determined. Five intermediate phases were found: a Nb3Ir, cubic, Cr3O type; tetragonal, ofecr thorhomhic, isostruc-turn1 with (ta-Rh); and a Nhlr3. cubic, AuCu, type. a Nb3lr and a Nbfr3 melt congruently; three eutectic and three pentectic reactions occur. The phase diagram of the Nb-Ir system had not been fully treated in the literature; only surveys of intermediate phases were found.1"5 In this study, the details of the phase boundaries were investigated as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS The experimental procedures such as arc melting of powder compacts, heat treatments, solidus measurements, X-ray, and metallographic observation were identical with those used in the work on the Nb-Rh phase diagram.&apos; They will therefore not be repeated here except where the conditions differed. The purity of the niobium powder was as stated in Ref. 6; the iridium powder of 99.9+ pct purity from J. Bishop and Co., Malvern, Penn., did not contain impurities exceeding 100 ppm, except rhodium (200 ppm). The melting points and vapor pressures of both elements are very similar. This fact contributed to a very small weight loss on melting and facilitated preparation of homogeneous alloys. As shown in Ref. 6 for Nb-Rh, no oxygen pick-up exceeding 200 ppm had to be considered; this was regarded as valid also for Nb-Ir. A total of forty one alloys were used in the determination of the phase diagram; their concentrations are shown in Fig. l, which presents the phase diagram. The concentration limits as determined by the weight-loss method averaged <0.2 at. pct, and never exceeded 0.5 at. pct. Heat treatments were carried out as described in Ref. 6. Depending on the concentration, only tantalum, tungsten, or iridium containers were employed, avoiding oxide crucibles altogether. Alloys from 0 to 25 and from 65 to 100 at. pct Ir were homogenized at 2095°C for 15 hr, intermediate compositions from 25 to 65 at. pct Ir for 65 hr at 1780°C. A typical annealing-time schedule is presented in Table I. Solidus points were measured as described in Ref. 6 with the modification that samples rich in niobium were held between pieces of tantalum foil and samples of high iridium concentrations were held between rhenium platelets or in iridium wire. After each run it was ascertained metallographically that no reaction with the holder had occurred. Rhenium was selected as holder material after it had been shown in separate tests that the melting points of Re-Ir alloys rise continuously from 2440°C. Metallographic examination was carried out as described in Ref. 6, and the same procedure and etchants were used successfully. While metallographic discrimination between a Nb3lr and o was easily possible, X-ray diffraction was necessary to separate al and ct2. X-ray powder patterns were taken and evaluated as for Nb-Rh6 yielding the error limits indicated in Table 111, to be introduced later. For the determination of the invariant reactions and phase boundaries, the same techniques as for Nb-Rh6 applied. The general accuracy of invariant concentrations is regarded as somewhat higher than for Nb-Rh due to the small slope of most solvus lines.

Jan 1, 1964

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.&apos; It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By Walter E. Hopper

(Wilkes-Barre Meeting, June, 1911.) I. LOCATION AND EXTENT. THE Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five rail-road-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. II. HISTORY AND DEVELOPMENT. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser " Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905, four wells were drilling. Great trouble was experienced with

Apr 1, 1911

By Albert J. Phillips

The effect of impurities on the flowsheet in the smelting and refining circuits for copper, lead and zinc is reviewed and the interflow of by-poduct metals from copper, lead and zinc plants is pointed out. The principal points of separation of all impurities in the circuits are indicated and the additional steps added to these circuits in order to effect impurity separation me shown. In this day and age, when difficult metallurgy is mentioned, one thinks of the extraction of more refractory or possibly the alkaline earth or rare-earth metals. It is true that the extraction of metals having a high affinity for oxygen and deleterious solubility for that element in the liquid metal, affords some of the most difficult extractive metallurgy problems. When this is coupled with an affinity for hydrogen, nitrogen, and carbon a devious approach is required that sometimes rivals the complexity of the metallurgy with which this paper deals. However, in all such cases the aim is for a simple

Jan 1, 1962

By B. H. Bergstrom, D. D. Crabtree, C. L. Sollenberger

Experimental data is given for several natural minerals on the load required for the fracture of single specimens over a very wide size range. The experimental results are compared with published data, such as for coal specimens from 30 to 64 in. in size. Correlations of the specific energy (per unit mass) required for fracture with specimen size are given as functions of specimen shape and the experimentally observed load-size relationships. These correlations are discussed with reference to comminution theory. Comminution, through compression or impact, can result only if sufficient force, or energy, is applied to a specimen of a given size. The relation of specimen size to force requirements has not been adequately considered previously. For single particle fracture, it was previously shown 1 that the specific energy (energy, e, per unit mass, M) at fracture of single glass spheres was inversely proportional to the product size modulus, k, as indicated in the equation: e/M = C/k [1] This was found true not only for numerous glass specimens of the same nominal size but was true for all nominal sizes tested from 1/8 to 1 in. Also, it was observed that the smaller spheres required a greater specific energy at fracture than the larger spheres and consequently had a smaller product size modulus. However, the relationship giving the required fracture energy as a function of specimen size was not further elaborated upon. This paper will extend the development of the feed size effect on specific fracture energy for brittle materials. SPECIFIC ENERGY-FEED SlZE RELATIONSHIPS FROM PREVIOUS DATA For the particular glass spheres tested in the previously described experiments,&apos; it can be shown, as on Fig. 1, that the specific energy varied inversely as the 4/3 power approximately of the feed size, F, in the span of nominal sizes ranging from 1/8 to 1 in. The load at which a 3-in. diam glass sphere (a crystal gazer&apos;s ball) was broken was within the range predicted by an extrapolation of this energy-feed size relationship. The product size distribution from this

Jan 1, 1963

By R. Kossowsky

BRIDGMAN has listed five possible transitions in bismuth at 25°C which were observed as volume changes. He was unable however to detect the last three transitions by electrical-resistivity changes. Kennedy and LaMori have verified the pressures at the Bi 1-11 and Bi 11-111 transitions. They suggested however that the 125-kbar transition previously reported by Bundy3 actually corresponds to the 90,000 kg per sq cm transition observed by Bridgman.1 Jura4 reported a well-defined drop in resistivity at 92 kbar obtained by a four-lead method. The Bi 111-IV and Bi IV-V transitions have not been reported in any of the above-mentioned references.&apos;-&apos; Bundy3 observed a small dent in the low-temperature boundary of the Bi Vll region which is consistent with the presence of a 111-IV boundary. Zeitlin and Bray-man5 were the only ones to report small but well-defined drops in resistance of bismuth at 44.0 and 63.8 kbar, corresponding to Bridgman&apos;s 111-IV and IV-V transitions, respectively. High-purity (99.99 pct) 0.020-in.-diam 0.5-in.-long bismuth wire was used to calibrate the Uniram tetra-hedral high-pressure apparatus used in the present work. The bismuth phase changes at 25°C were correlated with changes in electrical resistance as a function of pressure. The output of a sensitive bridge constructed of carbon resistors and kept at a constant temperature of ±°C during the measurements was fed to the Y axis of a MoseleyX-Y recorder and the X axis was used for time scans. Specimens were pressurized using a hydraulic press with maximum capacity of 200,000 lb. Load was applied in increments of 2000 lb and held for about 3 min. The resistance was recorded at the end of this time period. Good contact was established below 20,000 lb. Typical recorder charts are reproduced in Figs. 1 and 2 which show that resistance fluctuations were practically nil during each time scan. Well-defined discontinuities in resistance were observed at 58,000 and 82,000 lb, Fig. 1. Two small but definite "blips" are noticed at 92,000 and 122,000 lb, Fig. 2. At 156,000 lb another drop is observed which

Jan 1, 1967

By P. D. Hunt, B. Tani, M. G. Chasanov, R. Schablaske

The Zn-Vphase diagram was studied by thermal. metallographic, X-ray, and sampling techniques. Three ternary phase equilibria were observed: Mutual solid solubilities in vanadium and zinc appear to be negligible. The liquidus line is retrograde from 670° to 756°C. 1 HE only information in the literature relating to the Zn-V system was a study of corrosion of vanadium by liquid zinc&apos; and an examination of the effectiveness of zinc coatings in protecting vanadium-base alloys from oxidation at high temperatures.2 Establishment of the Zn-V phase diagram was undertaken as part of a study of transition metal solubilities in liquid metal solvents. Chemical, metallographic, thermal, and X-ray diffraction analyses were used to determine the diagram. MATERIALS AND EXPERIMENTAL PROCEDURES Vanadium (99.86 pct) in the form of powder and small chips was employed. Stick zinc (99.99 pct; major impurities: 10 to 15 ppm Pb and 20 ppm Cu) was used in the liquidus determinations and thermal analyses; zinc powder (98.80 pct) was used to prepare intermediate compositions. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The apparatus and sampling techniques were similar to those described by Martin, et al.3 The entire metal sample was dissolved to preclude analytical errors due to segregation on cooling. Vanadium was determined amperometrically, using iron (11) as the titrant,4 to an estimated accuracy of 1 pct. Standard techniques of thermal analysis were employed to examine alloy specimens contained in alumina crucibles under helium. Heating and cooling rates were about 1°C per min. At least five heating and cooling cycles over the range 420° to 700°C were performed for each of two Zn-15 pct V alloys. A Zn-0.2 pct V alloy was used in the determination of the eutectic temperature. The separation of intermediate phases from zinc-rich alloys was carried out by selective leaching with ammonium nitrate solutions. For further investigation of intermediate phases 1/4 in. diam powder compacts were prepared by pressing at 80,000 psi and were annealed in argon at 415" to 450°C for 10 days. Larger quantities of intermediate phases were prepared in sealed tantalum capsules heated in a rocking furnace. Temperatures were determined to an estimated accuracy of 0.5°C with a Pt/Pt-10 pct Rh thermo-

Jan 1, 1963

By K. Nassau

The Effect of tin and hydrogen on the C0 parameter of a titanium. specimens were capsule cooled in water to eliminate contamination by water. Deybe-Scherrer photograms were obtained in a 114.6 mm camera with CuKa radiation. The parameters shown in Table I and Fig. 1 were calculated from the 213 (8569°) and 302 (8173.5°) reflections? no attempt being made to correct for systematic errors. The principal difference in method of preparation of specimens between this investigation and that of Worner was the use of pickling by the latter to produce X-ray diffraction samples. The possibility that hydrogen introduced by pickling was responsible for the lower a and c-parameters was investigated with the same 80 pct HNO3- 20 pct HF solutions used by Worner. The 6 and 10 at. pct specimens, the parameters of which had already been determined, were pickled and the c-parameters obtained are also shown in Fig. 1. The a-parameters, not shown, are also diminished. The quality of the lines obtained from the unetched and etched samples was unchanged, being quite sharp in both cases. It is quite possible that if corrections for systematic error carried out that the parameters obtained for the unetched samples would approach the data of Worner. In any event, the parameters of the etched samples would be still lower. The data obtained here is evidence that hydrogen in solution has contracted the c and a -parameters. Crystallographic Angles of Calcium Tung-state (Tetragonal, c/a = 2.169) K. Nassau In connection with the preparation and orientation of single crystals of calcium tungstate (Scheelite -CaWO4), the need arose for a stereographic projection for this tetragonal material. There appear to be no tetragonal projections with a c/a ratio above that of indium1 (c/a = 1.522) in the literature. In addition to its use for calcium tungstate, such a projection might find other more general applications and is accordingly presented below. The most recent X-ray diffraction work on CaWO4 is that of Swanson, Gilfrich, and Cook,2 where a summary of previous work is also found. Lattice parameters given are: a = 5.242A, c = 11.372A, and c/a = 2.169. The material is tetragonal with space group Table I, giving angles between crystallographic planes (HKL) and (hkl), was calculated from the formula3

Jan 1, 1961

By R. W. Parsons

wben a displacement front encounters an isolated permeability heterogeneity, it will be perturbed. The details of this perturbation will depend on the beterogeneity size and shape, the Permeability contrast, and the mobility ratio. This paper deals with the displacement front behavior for one, simple, mathematically tractable model: a circular permeability discontinuity and unit mobility ratio. The progress of an initially planar front is shown for four permeability contrasts: k2/k1 = 0, 5/2, 2, m. The front distortion is more pronounced than streamline and isopotential distortion and it approaches a constant shape downstream from the discontinuity. INTRODUCTION The impact of reservoir heterogeneities on oil displacing processes depends upon the variation of the heterogeneous property (frequency distribution), its disposition (spatial distribution), and the inherent stability of the displacement mechanism.l The interplay of these factors plus the impracticability, if not impossibility, of describing a natural rock system in any detail makes exact displacement front movements difficult to determine. It is useful, however, to be able to qualitatively visualize what heterogeneities will do to a displacement front. In this respect certain simple models that can be treated analytically are of value. The following analysis will show the displacement front behavior for one such model. MODEL DESCRIPTION The flow field is two-dimensional and infinite in extent. The fluid flow is single phase, steady state and unidirectional at x, y = 2 m, or before insertion of the discontinuity. A circular permea- bility discontinuity is placed at the origin. Porosity and thickness are the same within and exterior to the heterogeneity. This is exactly the same model that was used by Greenkorn et al. to check analytically Streamlines as determined by Heie-Shaw flow models and finite difference computer techniques.2 FRONT POSITION CALCULATIONS The results of displacement front calculations are presented in Figs. 1 through 4 for four different permeability contrasts: k2/kl = O, %, 2, m. The times corresponding to the front locations are the Same for the 0 and cases! and for the 1/2 and 2 cases. The determination of front positions at various times is based on known analytical expressions for velocity potentials ().2 and stream functions ().2 These expressions are in terms of the x and y

Jan 1, 1969

By Frank Foote, Eric R. Jette

In a recent article,1 the authors reported the results of an X-ray investigation on the range of solid solutions that occurs in the iron-oxygen system in the vicinity of the compound FeO, which frequently is called "wüstite." The object of that investigation was primarily to study the unusual type of solid solution phenomena involved in this range. Briefly summarized the results were: 1. The NaCl type of lattice found by earlier workers was confirmed. 2. The lattice dimensions decrease rapidly with decrease in iron content. 3. No alloy that was a homogeneous single phase was ever found at compositions beyond 76.80 per cent Fe, while the theoretical iron content of FeO is 77.73 per cent Fe. 4. Measurements of the densities and lattice constants led to the conclusion that the form of substitution was complex, an FeO group being replaced by oxygen. Such a substitution, of course, is equivalent to removing an iron atom (or ion). The ideal unit cell of FeO can be considered as containing four groups of FeO and, thus, when this type of substitution takes place, there remain in the unit cell three FeO groups and an oxygen, or a total of seven atoms with a gross formula of Fe3O4 instead of the original Fe4O4. 5. This was the only interpretation that would fit the experimental results and at the same time be consistent with (a) the previously determined fact that the FeO lattice is ionic (i, e., consists of Fe++ and O? ions) and (b) the chemical fact that as the oxygen content of the substance increases, ferrous iron becomes oxidized to ferric iron. The experimental results of this investigation are included in Fig. 1. The purpose of the present investigation was to determine the limits of this homogeneity range by means of the X-ray structure analysis. This method has been applied frequently to the study of solid solutions by Westgren and his coworkers as well as by other investigators. The principle is simple: if the change in lattice constant with composition is

Jan 1, 1933

By M. Gensamer, B. Lustman

A recent paper described, by means of stereographic pole figures, the preferred orientations produced by cold-rolling low-carbon steel of automobile-body grade. It was found that the surface of the sheet exhibited a deformation texture significantly different from the texture possessed by the inside of the sheet. Efforts to produce the surface texture by buffing a sample exhibiting the normal or inside texture, using a copper lap, have not been successful. In view of the data collected by Kurdjumow and Sachs2, it was suggested that the surface texture might be the result of partial recrystallization of the normal or inside texture. The recrystallization texture of cold-rolled mild steel was studied by Goss3, but he did not use the pole-figure method, so that his conclusions were in need of verification. For these reasons the work reported in here was undertaken. It had two objectives: (1) to study the general behavior of cold-rolled mild steel on recrystallization below the critical temperature Al, and (2) to attempt experimentally a demonstaration of the genesis suggested above for the surface texture in cold-rolled steel. The material was that used by Gensamer and Mehl, cold-rolled to 97.5 per cent reduction in thickness. Fig. 1 is an X-ray pinhole photo-gram of this material, taken with the beam transmitted perpendicular to the plane of the sheet, using a molybdenum target at 35 kv. with no filter. It is typical of the inside texture, but in it the deformation texture is better developed than in the samples that showed a well developed difference between the inside and surface samples. Specimens from this sheet, which was 0.005 in. thick, were annealed for 5 min. at various temperatures in a lead bath. After about 0.0005 in. had been etched from both surfaces, X-ray photograms were prepared, using the technique described in the earlier paper1. Figs. 2 to 6 are photograms of the annealed sheet, at 566, 571, 577, 580 and 650" C. (1050&apos; to 1202" F.), in order. Fig. 2 shows that 5 min.

Jan 1, 1937

By R. M. Treco

THE thermal expansion of pure beryllium was first investigated by Hidnert and Sweeneyl in 1925 on a single cast specimen stated to be of 98.9 pct purity. A study of the coefficients of expansion by X-ray methods has recently been made by P. Gordon&apos; on powder obtained from the Brush Beryllium Co. assaying 97 wt pct beryllium with about 2 wt pct oxygen as an impurity. The present work pertains to about the highest purity metal obtainable from the Brush Beryllium Co. This metal was in the form of lumps which were remelted and cast in a high-vacuum induction furnace. Expansion data in this paper deal with beryllium extruded into bars of rectangular cross-section 4x1/2 in. and the anisotropic expansivity of a large cast single crystal. Analysis of the cast metal after extrusion indicated a beryllium assay of 99.28 pct. Impurities were 0.170 pct Fe, 0.140 pct Al, 0.014 pct Mg, 0.086 pct Si, 0.020 pct Cu, 0.020 pct Mn, 0.007 pct Ni, 0.007 pct Ca, 0.080 pct C, 0.179 pct 0, (as BeO). Part I—Extruded Metal Thermal expansion measurements were obtained with a fused quartz-tube differential type dilatom-eter3 on specimens cut from the extruded sections in longitudinal and transverse directions. Specimens were machined to a diameter of 0.250 in. and a length of 3.000 in. One sample from each direction was vacuum annealed for 1 hr at 800°C. The dilatometer tube was placed in a vertical tube furnace having a uniform temperature zone which was twice the length of the sample. Average time for a complete thermal cycle to 500°C was 18 hr. Temperatures were observed with two chromel-alumel thermocouples attached to the sample about 1 M in. apart. The accuracy of temperature measure-ment was ± 0.25°C. An argon gas atmosphere sur-rounded the specimen to prevent oxidation of the beryllium. Samples were identified as shown in table I. Results - The original plan included measuring expansion up to 1000°C, but the first two runs on sample No. 5 showed that a permanent contraction occurred from

Jan 1, 1951

By David N. French

In a recent paper, Miyoshi, Hara, and sugimotoL have shown that hardness increases and crack resistance decreases with polishing time in tungsten car-bide-cobalt alloys. They attribute the changes in hardness and crack resistance to cold working in these alloys. More recently Exner2 explains the decrease in crack resistance with the amount of material removed (polishing time) by suggesting that polishing removes a high compressive residual surface stress due to the initial grinding operation. He cites previous work on steel to show grinding can induce surface compressive stresses but offers no direct experimental measurements to support this in cemented tungsten carbides. In recent work we have observed changes in residual stress in the W C phase as measured by X-ray diffraction techniques with changes in polishing conditions.3 As a result of the work of Miyoshi et al.,L a brief study was undertaken to investigate the effects of polishing and grinding on the residual stress in the WC phase and have been reported.4 A single composition of tungsten carbide —10 wt pct Co was used. Two initial conditions were studied: an annealed condition with about -30,000 psi residual stress from the differences in thermal coefficients of expansion of WC and cobalt and, on the same specimen, a surface ground with a 150 grit diamond wheel. Stress was measured in the WC phase using X-ray diffractometry as a function of the amount of material removed by metallographic polishing with 6 diamond paste. The results are shown in Fig. 1. Two things are noted, 1) polishing with 6 p diamond paste has little effect on the annealed sample and 2) the magnitude of the grinding stress is markedly reduced as material is removed. By the time 0.1 mil is removed the surface has a metallographic polish satisfactory for light microscopy examination. Thus the surface, even though polished, can still retain most of the stress due to grinding. Since WC is itself slightly ductile, it seems reasonable that high compressive stresses can be generated in the surface by the plastic deformation accompanying grinding. Exner2 suggests, by analogy with steel, that as a result of grinding both WC and cobalt in the

Jan 1, 1970

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

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.&apos; The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970