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By Paul Gordon, A. S. Iyer

Apreliminary investigation has been carried out on the annealing behavior of explosively deformed copper as compared to that of conventionally deformed copper, using hardness, stored energy, and the sharpening of X-ray spots on Debye rings as the measures of annealing. Some metallographic observations were also made. Two purities of copper were studied. The first was tough pitch copper obtained as a small piece from the guard ring of a sample explosively deformed to approximately 500 kbars.* The second consisted of mentedand deformed these samples quite badly so that only a few small fragments were available for the annealing experiments. As a result, little in the way of quantitatively significant data was gleaned from the measurements. However, several important qualitative differences between the annealing of explosively deformed and conventionally deformed copper have been observed. It is these effects which are described in this report. Fig. 1 presents the results of hardness and stored energy measurements during the annealing of the high-purity copper after explosive and after conventional deformation. The data for the conventionally deformed copper were taken from the work of Gordon;' in this copper it is evident that most of the stored energy is released concommittantly with the hardness drop. As shown in orddon's' investigation, these effect:: are definitely associated with recrystal-lization. In the case of the explosively deformed copper, on the other hand, a large fraction of the stored energy is released before any appreciable hardness change takes place. At 160°C about 40 pct, and at 170°C about. 80 pct, of the stored energy appears to have been released prior to the onset of softening, i.e., undoubtedly prior to recrystallization. In view of the facts that the hardness and energy measurements were made on separate samples and that there is reason to suspect that the intensity of the explosive deformation from sample to sample may not have been uniform, a check run was carried out in which both energq release and hardness changes were measured cnn the same sample. The results of this run, shown in Fig. 2, confirm the conclusion that much of the stored energy is released before the hardness begins to change appreciably. In an effort to obtain some idea of the activation energy associated with the early release of energy, a single callorimetric sample was annealed in two steps, first at 149.5"C and then at 159.5"C, Fig. 3.

Jan 1, 1962

By W. M. Peirce

WITH the supply of zinc, like that of most other nonferrous metals, inadequate to meet the demand, efforts to increase domestic ore supplies and production capacity have been of primary interest. No major sources of new ore have been disclosed during the year but improvements have been reported in facilities for mining and concentrating ores from existing mines. The American Zinc, Lead and Smelting Co. has announced its intention of erecting a new mill in the Ouray district of Colorado. The Consolidated Mining and Smelting Co. of Canada is reported to be planning improvements costing $3,000,000 to its Sullivan mine and concentrator at Kimberley, B.C., where the sink-float process is to be used for preliminary ore treatment. In the reduction field, the St. Joseph

Jan 1, 1947

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By K. D. Jacob, W. L. Hill

Fluorine recovery in the United States has been restricted chiefly to manufacture of ordinary superphosphate and wet-process phosphoric acid. However, there is an expanding use of fluorine by industry in the form of hydrofluoric acid. Improved methods for recovering fluorine from phosphate rock would yield an adequate supply of fluosilicates and a substantial contribution to the hydrofluoric acid requirement. THE bulk of natural phosphates is comprised of calcium phosphates, which are usually apatites;' calcium aluminum phosphates such as pseudowavel-1ite; and aluminum phosphates, which occur in extensive deposits, notably on Grand Connetable Island." Nearly all deposits of current commercial value are apatite, often with admixed material of other classes. In the trade coarsely crystalline material, mainly fluorapatite of igneous origin, moves as apatite, whereas the fine-grained material of sedimentary origin is marketed as phosphate rock. The latter classification includes the phosphate shales in western North America. Although several genetic varieties of phosphate rock are recognized, most known reserves are of marine origin. Calcium phosphate is concentrated from Florida land pebble and Florida hard rock deposits and from Tennessee brown rock deposits. Phosphate Rock as a Fluorine Carrier: More than two decades ago Reynolds and Jacob surveyed the fluorine content of commercial phosphate rock from various parts of the world. Later these samples were re-analyzed by a new and more reliable method of determining flourine. The revised results with interim additions of new samples, published a few years ago in a brief summary," are shown in Figs. 1-3. Through the points representing the respective varieties of rock medial straight lines are drawn. In some instances the lines are well defined by the points; in others, where scattering renders the position of the best line uncertain, the greater weight is given points near the end of the covered range. Wherever distinct varieties are not recognized among regional deposits the custom is to identify the sample with the geographical location of the deposit. Although all rock varieties cannot be classified with certainty, the plotted results exhibit three distinct types of rock in which the F to P2O5 ratio diminishes, remains sensibly constant, and increases, respectively, as the grade of rock increases. Existence of two types of Florida land pebble, Fig. 1, is supported by additional results recently supplied by a producer." Generally speaking, phosphate rock from continental deposits carries considerably more fluorine, and apatite and insular phosphates less, in proportion to the phosphorus content than is required by the formula for fluorapatite. Exceptions to this are apatite from Canada and certain samples of Florida waste-pond phosphate. The manner in which excess fluorine is held and the nature of the carbonate in carbonate apatite are discussed in recent articles. High-grade calcium phosphates with F to P2O5 ratios less than 0.05 have been found in Curacao, Christmas Island," Mexic,13 and elsewhere. The calcium aluminum phosphates and aluminum phosphates aften carry notable amounts of fluorine. The F to P2O, ratio for one sample of pseudowavel-lite concentrate was 0.05." Aluminum phosphate from Grand Connetable Island is very low in fluorine, whereas some aluminum phosphate minerals" carry as much fluorine as highly fluorinated phosphate rock. Fluorine in Domestic Phosphate: The curves shown in the figures permit interpolation of the F to P2O5 ratio corresponding to the midpoint of selected ranges in grade of any one of the several varieties of phosphate. Multiplication of the interpolated ratio by the mid-range grade (P2O5) yields a figure for the percentage of fluorine in this grade. Then, with the use of the mid-range grade, the amount of fluorine held in phosphate reserves can be estimated, see Table I. Accordingly, on Jan. 1, 1950, the fluorine complement of known domestic reserves exceeded 420,000,000 long tons of the element. A previous figure," deduced in 1940 by a simpler procedure

Jan 1, 1955

By Bailey, Lewis Newton

Bailey, Lewis Newton, Master Engineer, Senior Grade, 4th Regiment, U. S. Engineers, Headquarters Company, died of pneumonia at Camp Merritt, N. J., on Apr. 30, 1918. Baird, Louis, Lieut., Royal Field Artillery, British Army, died on the battlefield in 1915. Ballamy, John H., Capt., 103d Engineers, killed in action near Fismes, Aug. 9, 1918. Bowles, Martin F., 2d Lieut., Co. B, 355th Infantry, killed in action, Sept. 3, 1918. Burt, Andrew, died in active service, 1916. Cobeldick, William Morley, Royal Engineers, died from gas poisoning on Oct. 7, 1915. Dougall, Ralph, 4th University Co., Princess Patricia Regiment, killed in action early in the war. Evans, Alfred Winter, Lieut.-Col., New Zealand Rifle Brigade, D. S. 0., D. C. M., killed in action on Oct. 12, 1917.

Jan 3, 1919

By Charles Wurms, Robert Steinitz

DURING an investigation to determine the compatibility of several metals with tungsten, the degree of reaction between tungsten and lead was determined. A literature survey showed considerable disagreement between the results of various earlier investigators. Information presented by M. Hansen1 states that, according to S. Inouye,2 tungsten has very poor resistance against attack by molten lead, even at the low temperature near the melting point of lead. A phase diagram in the same reference indicates a solubility of 30 wt pct W in molten lead at 1300°C. Contrary evidence was shown by Parkman and shepard3 in their investigation of materials for use in heat transfer systems containing liquid lead alloys; they performed experiments at 980°C for times up to 50 hr without noticing any appreciable attack on the tungsten. Tungsten sheet was immersed in molten lead contained in Vycor tubes evacuated to at least 10-4 mm Hg. R. Bernard4 and R. I. Jaffee5 also indicate that no reaction occurs between molten lead and tungsten. However, no experimental data were included in these reports. In order to settle the question of the solubility of tungsten in molten lead, tungsten powder with an average Fisher subsieve particle size of 6µ was pressed in a double-acting die at 6 tsi to small compacts. They were then sintered in an atmosphere of hydrogen for 2 hr at 1700°C, resulting in a sintered density of 64 pct of theoretical with final dimensions of 0.260 in. in height and 0.245 in. in diameter. For all tests, the tungsten pellets were immersed in molten lead. Table I is a summary of the experimental procedures showing atmospheres, temperatures, and times. The first experiments were performed at 650°C; at this temperature, the liquid lead should wet the porous tungsten better than at its melting point, and penetrate into the pores. The lead was heated in a graphite crucible with a graphite cover. No protective atmosphere was used, as it was expected that the formation of CO would be sufficient to prevent oxidation. This, however, proved to be wrong, and all tungsten samples showed a slight oxide film after treatment. The tungsten samples were immersed in the molten lead for times of 5 min, 10 min, 1/2 hr, 1 hr, and 2 hr. After this time, the melt was poured into a form and the

Jan 1, 1962

By H. W. Imholz

Active interest in the North Central Texas area centered in the development of the Palo Pinto limestone-producing zone, near the town of Avoca, in the northeast part of Jones County. This producing horizon was discovered in 1937, in the Iron Mountain Oil Company's well No. 1 Olander, in sec. 196, B.B.B. & C. survey, at 3238 to 3250 ft. During the development of this pool, it was generally referred to as the Avoca pool. As a second pool has been discovered in the same producing zone, also near the town of Avoca, the writer has taken the liberty of changing the name of the original Avoca pool to Avoca-Olander pool. Forty producers had been drilled in the Avoca-Olander pool by the end of 1938; their initial ranged from 28 to 300 bbl. per hour. Stimulus was given to the interest in the development of the Palo Pinto limestone when the Ungren-Frazier No. 1 Griffin, in sec. 199, B.B.B. & C. survey, Jones County, found the limestone from 3225 to 3250 ft., with an initial production of 931 bbl. per day. (This new pool has been given the name of Avoca-Griffin pool, by the writer.) The best well to be completed, up to the present time, is the Bert Fields No. 1 Taylor in sec. 199, B.B.B. & C. survey, which had an initial production of 748 bbl. in 3 hours. The Owen-Snebold No. 1 McKeever in sec. 158, B.B.B. & C. survey, in northwest Shackelford County, added to the interest in the Palo Pinto limestone when it extended the Ivy pool with a well in the Palo Pinto limestone from 3145 to 3183 ft., and was estimated good for 6,000,000 cu. ft. of gas and 6000 bbl. of oil per day. During 1938, Stonewall County obtained its first commercial producer when the Stonewall Oil Co. in No. 1 Parriott discovered the Palo Pinto limestone saturated from 5169 to 5176 ft. and tested 371 bbl. per day. Two new producing horizons were discovered about 2 miles east of the old Noddle Creek pool, Jones County; the first, the Humble Oil & Refining Co. No. 1 Irvin, in sec. 48, block 18, T. & P. R. R. Co. survey, which had saturated limestone from 2550 to 2567 ft. and was good for 100 bbl. per day; the second, in the Humble No. 1 Horton, sec. 40, which

Jan 1, 1939

By H. W. Imholz

Active interest in the North Central Texas area centered in the development of the Palo Pinto limestone-producing zone, near the town of Avoca, in the northeast part of Jones County. This producing horizon was discovered in 1937, in the Iron Mountain Oil Company's well No. 1 Olander, in sec. 196, B.B.B. & C. survey, at 3238 to 3250 ft. During the development of this pool, it was generally referred to as the Avoca pool. As a second pool has been discovered in the same producing zone, also near the town of Avoca, the writer has taken the liberty of changing the name of the original Avoca pool to Avoca-Olander pool. Forty producers had been drilled in the Avoca-Olander pool by the end of 1938; their initial ranged from 28 to 300 bbl. per hour. Stimulus was given to the interest in the development of the Palo Pinto limestone when the Ungren-Frazier No. 1 Griffin, in sec. 199, B.B.B. & C. survey, Jones County, found the limestone from 3225 to 3250 ft., with an initial production of 931 bbl. per day. (This new pool has been given the name of Avoca-Griffin pool, by the writer.) The best well to be completed, up to the present time, is the Bert Fields No. 1 Taylor in sec. 199, B.B.B. & C. survey, which had an initial production of 748 bbl. in 3 hours. The Owen-Snebold No. 1 McKeever in sec. 158, B.B.B. & C. survey, in northwest Shackelford County, added to the interest in the Palo Pinto limestone when it extended the Ivy pool with a well in the Palo Pinto limestone from 3145 to 3183 ft., and was estimated good for 6,000,000 cu. ft. of gas and 6000 bbl. of oil per day. During 1938, Stonewall County obtained its first commercial producer when the Stonewall Oil Co. in No. 1 Parriott discovered the Palo Pinto limestone saturated from 5169 to 5176 ft. and tested 371 bbl. per day. Two new producing horizons were discovered about 2 miles east of the old Noddle Creek pool, Jones County; the first, the Humble Oil & Refining Co. No. 1 Irvin, in sec. 48, block 18, T. & P. R. R. Co. survey, which had saturated limestone from 2550 to 2567 ft. and was good for 100 bbl. per day; the second, in the Humble No. 1 Horton, sec. 40, which

Jan 1, 1939

By B. W. Adams, R. W. Shilling

9.4-1. Basic principles. DESCRIPTION AND BASIC FUNCTIONS. The concept of inclined skip haulage is not new. The basic idea has been in use at least 400 years. The system is essentially a steeply inclined railway utilizing a hoist to pull the skips to the top or intermediate positions. Inclined skip haulage is often justified where high lifts would require long hauls for other haulage systems. The basic system types are as follows: 1. Single skip, single drum. This system is a single car pulled by a simple hoist system. 2. Balanced skip, single drum. A system utilizing two cars (skips on cables)--one overwound, one underwound-on a single drum. The dead weight of one skip and cable balances the dead weight of the other. As one skip ascends the other descends between two fixed points. 3. Balanced skip, double drum. This system is an elaboration of system No. 2, except the drums may be disengaged from one another to permit the skips to service various loading and dumping points. The preceding are major classifications subject to numerous variations. These variations may be in the skipway, skip design, loading methods, or unloading methods. A few examples follow: 1. The skipway may be standard or special railroad, an overhead monorail or cable, or a ramp for rubber tired vehicles. 2. The skip, per se, may be of varying dumping arrangements (side, bottom, etc.) or could be the box of the vehicle hauling to the skip. 3. Loading may be accomplished directly from the service unit to skip, through an intermediate loading device (e.g., a pocket), or into bins which feed the skip. Loading may be at more than one point. 4. Unloading of the skip can be simple or complex as required. Dumping may be to the haulage unit, to bins and feeders, or to a crusher and conveyor system. Dumping may take place at more than one point.

Jan 1, 1968

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

A tentative plan for the Colorado Meeting has been formulated as follows: One day will be spent at Denver, one day at Colorado Springs, one day at Cripple Creek, a trip by automobile to the top of Pike's Peak, one day at Pueblo, one day at Leadville. All the principal mines and mills of the districts mentioned will be visited, including the gold mines in Cripple Creek, the lead, zinc, and steel works. of Pueblo, the production of ferro-molybdenum by electric furnace at Leadville, etc. Special arrangements are being made for the social entertainment of ladies at all points; one evening at Colorado Springs will be devoted to a reception and dance, and the usual dinner will he given on another evening. The following papers have already been accepted for the Colorado Meeting, and some have already been published: Fireproofing Mine Shafts by the Anaconda Copper Mining Co. By E. M. Norris. (March Bulletin.) Air Blasts in the Kolar Gold Field, India. By E. S. Moore. (March Bulletin.) The Use of Coal in Pulverized Form. By H. R. Collins. (April Bulletin.) Coal Mining in Washington. By F. A. Hill. (April Bulletin.) Carbocoal. By C. T. Malcolmson. (May Bulletin.) Gaging and Storage of Oil in the Mid-continent Field. By O. U. Bradley. (March Bulletin.) An Interpretation of the So-called Paraffin Dirt of the Gulf Coast Oil Fields. By A. D. Brokaw. (April Bulletin.) The Theory of Volcanic Origin of Salt Domes. By. E. DeGolyer. (May Bulletin.)

Jan 5, 1918

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

DURING the past few years there has been considerable effort devoted to the understanding of radiation effects on materials. The concept of the Frenkel defect and other lattice defects suggests that radiation may alter the rate of many metallurgical phenomena, especially those which are diffusion controlled. In 1953 R. R. Coltman and T. H. ~lewitt' found an appreciable effect on the ordering rate of Cu,Au due to fast neutron bombardment. Since then several rather comprehensive theories have been proposed on radiation enhanced diffusion in solids.2"4 If the energy of the radiation is above the threshold energy for the removal of atoms from their lattice sites, Frenkel defects will be produced. These defects can be produced uniformly throughout a relatively thick specimen by high-energy X-rays permitting bulk property studies without the limitation of sample dimensions. In this work high-purity arsenic containing 30 ppm of impurities was allowed to diffuse from the gase- ous phase at 700°C into single crystals of p-type germanium containing 0.1 ppm of indium. As the arsenic diffuses into the P-type germanium, an n-type layer will form in the diffusion zone. At the p-n junction the concentration ratio of the arsenic to the indium is constant. Experimental Procedures—The germanium specimens, 10 mm by 10 mm by 5 mm, were polished and etched to a mirror finish. The specimens were then sealed off in a vycor glass capsule at 3 x 10"5 mm Hg pressure with a sufficient amount of arsenic powder to produce a one-half atm pressure of arsenic at 700°C. Specimens were annealed at 700°C without radiation. The diffusion coefficient determined from these samples agrees within 8 pct of previous work done by Fuller.' Three specimens were given diffusion anneals at 700°C in a small tube furnace centered beneath the target of a 2-mev Van de Graaff generator. The specimens when in the furnace were 10 cm directly below the target of the generator. These specimens were irradiated continuously during the diffusion run with the Van de Graaff operating at 2 mev with a tube current of 225 to 250 pamp. The intensity of the x-radiation at the surface of the specimen inside the furnace was approximately 4.5 x l05 roentgens per hr. The temperature was controlled within m2°C by a chromel-alumel thermocouple throughout this work with no observed temperature change due to the radiation. By careful lapping, the samples were polished at an angle of 5 deg to the diffusion zone, giving a XI0 increase in the visible diffusion zone. The location

Jan 1, 1960

By H. W. Paxton, G. M. Pound

A method is outlined for taking into account variation in chemical potential of both components in evaluating capillary effects at growing interfaces. The results are compared with experiment, and seem to be in reasonably good accord for Widman-statten ferrite growing in austenite. ENERY pointed out that during the steady-state growth of phases with a rather small radius of curvature at their advancing edge capillarity cannot be neglected. By proper application of the Laplace equation a correction must be made to the activity gradients down which diffusion occurs. Subsequent workers have concerned themselves with attempts to evaluate specific cases by the use and modification of the principles laid down by Zener.2-5 To solve the problem in its simplest form it is necessary to assume thermodynamic equilibrium at the interface and to select some criterion which will allocate the available free energy between reversible and irreversible processes. Zener chose to assume that the division should be made such that the new phase grew at the maximum rate. Other workers have used the same2,3 or different assumptions, e.g., maximum rate of free-energy dissipation,4 minimum rate of entropy production.5 Li6 has proposed that the "thermokinetic potential" should be a minimum at steady state. The purpose of this presentation is to note that most prior treatments have considered variations due to capillarity only in the chemical potential of the mobile constituent, and that a more consistent treatment must involve a consideration of the variation of chemical potentials of both solute -and sol- vent in a binary system.* As an example, the way in which this arises for ferrite growing from austenite may be illustrated by reference to Fig. l(a). The line OABC shows a typical variation of carbon activity with composition at one atmosphere pressure (at a transformation temperature below A3). In the tip of a growing ferrite plate with a hemi-cylindricab leading edge of radius ?, the pressure due to capillarity is*

Jan 1, 1963

By J. O. Betterton, W. M. Spicer

The solubilities of antimony in the a and ß-forms of zirconium were determined between 750" and 1300°C. The a-phase forms by a peritectoid reaction, and the a/(a + ß) and ß/(a + ß) phase boundaries rise in temperature with in- ' creasing antimony. Impurities in the 99.95 pct zirconium were sufficient to influence the phase boundaries and the variation reported is approximate. The restricted solid solubility of the terminal zirconium phases, which is especially characteristic of this system, is thought to result from the low free energy of the Zr2Sb phase. ZIRCONIUM-antimony alloys are important in zirconium alloying studies since antimony is one of the highest valent elements which can be used to make zirconium alloys. The dilute alloys are of further interest as they have somewhat better corrosion resistance' than pure zirconium. The first investigation of the phase diagram was made by Russi and wilhelm2 who found a eutectic reaction, liquid (- 17.5 at. pct Sb) = ß zirconium (- 11 at. pct Sb) + Zr2Sb, at 1430°C'. The Zr2Sb phase was of complicated hexagonal structure, and by thermal analyses of the relatively impure alloys then available, Russi and Wilhelm found evidence for the peritectoid formation of the a-phase. EXPERIMENTAL In the present work, the phase diagram was re-investigated in the region 0 to 5 at. pct Sb and 750" to 1300°C using iodide-zirconium alloys. Details of the procedure have been described earlier. Essentially the alloys were prepared by arc casting and were then examined by the annealing and quenching method. The times of annealing varied from 1 hr at 1300°C to 30 days at 760°C. As in other zirconium phase-diagram studies1"5 the impurities in the zirconium were still sufficient to affect the results, and the experiments will therefore be described in 3 parts. The results from the first 2 parts of the work are shown in Fig. 1. Here the ß/(ß + Zr2Sb) and a/(a + ZrzSb) phase boundaries were determined with alloys made from 99.9 pct zirconium,* and cast under such conditions that the Vickers hardness of a alloys extrapolated to 95 to 110 VPN at 0 at. pct Sb. Such alloys were not suitable for investigations of the (a + ß) region, and the results shown in Fig. 1 near the (a+ ß) and (a +ß + Zr2Sb) regions were determined with purer alloys. These alloys had an extrapolated hardness range of 75 to 85 VPN and were made from 99.95 pct zirconium. A deviation from binary equilibrium occurs in Fig. 1 as indicated by the (a + ß) region of pure

Jan 1, 1959

By J. G. Savins

Analytical procedures are described for optimizing the selection of a rheological model when it is desired to express the functional relationship between true shearrate and shearing stress in analytical form. The procedures are extended to two principal model categories — "Generalized Newtonian" and "Viscoplastic" models. Graphical examples are presented to illustrate the utility of certain characteristic deriuative functions in distinguishing between these categories and in determining how well a particular model reflects the flow behavior of rheologically anomalous materials in simple shearing flows. INTRODUCTION Modern drilling fluids and fracturing fluids, being chemically complex, are frequently non-Newtonian — a peculiarity which complicates the solution of problems such as designing flowline and process equipment, and predicting laminar-turbulent behavior, solid-suspending ability and cutting-transport efficiency. Therefore, techniques of data analysis which accurately characterize the behavior of rheologically complex materials are needed for the accurate formulation of solutions of these and similar problems. It is the purpose of this paper to describe the application of a sensitive method of rheological data analysis — the dual differentiation-integration method of optimizing the selection of the functional relation between shear rate and shearing stress — to a variety of materials of interest in drilling and production practices. BASIC CONCEPTS THE DIFFERENTIATION METHOD To a first approximation, the viscosity function for a non-Newtonian system can be expressed in a form analogous to Newton's law of viscosity by the following generalization2.3 between the stress On introducing the restrictions that the system is incompressible and the motion is rectilinear, then l = 0 and l3 = 0 ; and with the further restriction that the flow is slip-free, the viscosity (an invariant) is then determined solely by 12. With this approach one can set up a suite of integral equations relating observed kinematical and dynamical parameters for certain types of flow experiments involving simple shearing motion, e.g., flow in a cylindrical tube, flow between rotating concentric cylinders, and flow between fixed parallel surfaces of large aspect ratio. Taken in the order cited, these integral equations are as follows.

By Walter Weeks

CONSIDERABLE difference of opinion seems to exist as to whether the rate of air flow when a fan is placed on a given duct should be determined by the use of static pressure or total pressure characteristics. A little study will show that both methods are correct. Assume that a fan is connected to a duct by an expansion piece as shown in Fig. 1, and that steady flow is established. Considering the atmospheric pressure as zero pressure, let the static head at the outlet of the fan be h and the velocity at this point be v1. The total head at the outlet is then h + v1/2g? The total head at this point must be equal to the total head at the end of the duct plus the losses that have occurred between the two points. Let f be the friction loss in the straight duct, s the shock loss in the dif- fuser, and V2 the velocity at the end of the duct. Then h+ v12/2g=v22/2g + f + s FIG. 1.-FAN ON DUCT. A curve showing the value of the left-hand side of the equation for different rates of flow is the total pressure characteristic of the fan, while a curve showing the value of the right-hand side is the total pressure characteristic of the duct. If these two curves are plotted on the same chart, the intersection indicates the rate of flow when steady flow is established.

Jan 1, 1930

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By E. A. Peretti

BEFORE embarking on a detailed investigation of the system indium-antimony-bismuth, experiments were carried out to determine the existence of quasi-binary sections. The bordering binary systems are known1 and show the occurrence of three intermetallic binary species corresponding closely to InSb, InBi and In2Bi. Attention was focused on the low-indium end of the ternary diagram where the possible quasi-binary sections, excluding ternary compound formation, would involve the pairs: InSb-Bi, InBi-Sb and InSb-InBi. The latter pair revealed itself as a true quasi-binary, so it was investigated fully by thermal analysis, x-ray and microscopic examinations. All compositions were made by proper combination of three elements involved. The indium had a guaranteed purity of 99.97 pet; the antimony contained 99.99 pet Sb, and the bismuth had a purity of 99.99 pet. Alloys were made by melting together antimony, bismuth and indium in evacuated, sealed pyrex-glass tubes at a temperature of 600°C with vigorous agitation. The melts, weighing about 80 grams, were allowed to freeze in the sealed tubes and finally were transferred to glass tubes for the taking of cooling and heating curves. A protective atmosphere of helium was used, and the melts were stirred mechanically while cooling at rates of from 0.5 to 3°C per min. Temperatures were measured with a calibrated chromel-alumel thermocouple and were recorded graphically on a Minneapolis-Honeywell extended-range recorder working in conjunction with a Leeds and Northrup type K-2 potentiometer. Conventional polishing techniques gave satisfactory results in preparing specimens for microscopic examination. Etching was carried out with Vilella's reagent or aqueous mixtures of chromic oxide with either nitric acid or sulfuric acid plus dichromate. Conclusions deduced from the thermal analysis and microscopic examinations were confirmed by X-ray photograms using Co-K alpha radiation. The phase diagram is shown in Fig. 1. The liqui-dus consists of an uninterrupted line running from the freezing point of InSb (525°C) to a eutectic point experimentally indistinguishable from the freezing point of InBi (110°C). X-ray patterns of the InSb show a slight expansion of the lattice with the addition of InBi, and microscopic work indicated the solid solubility of InBi in InSb to be less than 0.5 pet at room temperature. Acknowledgment We wish to thank the Indium Corporation of America for the loan of the indium used in this investigation. References 1 E. A. Peretti and S. C. Carapella, Jr.: Trans. ASM., 1949, vol. 41, P. 947. T. S. Liu and E. A. Peretti: Trans. ASM, 1952, vol. 44, p. 539. Metals Reference Book, vol. 1, 2nd ed., AIME, p. 345.

Jan 1, 1959