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By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,' in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young's modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

By W. W. Beddow

TWENTY years or so ago I wrote an article on management which consisted mostly of a chart similar to thousands of others of that day showing line functions, staff functions, and the chain of command in a typical mining organization. Since hen we have been "bossing" from the faces to the swivel chair and we have made many errors of no little expense to our companies. We have kept the chart in mind but many times we have changed the functions to fit the people we have had to work with. Good management after all is getting results with the people, the equipment, the supplies, and the natural conditions of the coal seam or seams and adjacent strata present. We have made, with little effort, a good showing with average people and equipment in good natural conditions. We have made a miserable showing (although expending every personal effort) with better than aver- age people and equipment in bad natural conditions. In the latter case many of our stockholders felt that better management would have found some way to save their investment. Perhaps they were right.

Jan 1, 1944

AlFred JamEs," London, Eug.:—I thank you, gentlemen, for Sour kind invitation to address you. It is a very great pleasure for me to be here at your annual meeting, and, although I have been a member since 1894, this is the first opportunity I have

Jan 1, 1909

By R. G. Treuting

Germanium single crystals strained in tension at 600°C slip on the {Ill} plane and, macroscopically at least, in the <110> direction. Deformation is in homogeneous: various localized rotations are observed, as is a banding consistent with secondary slip banding. The structure after deformation is polygonized with a domain size of about 2x1O-3 cm. In relaxation tests, an incubation period prior to flow is observed, of duration inversely related to temperature and applied stress. Under continuous loading, there is a sharp first yield point. A critical resolved shear stress therefore must be cited with respect both to temperature and to rate of loading. At 600°C, when loading proceeds at 2900 psi per min, it is 1310 psi. The yield point phenomenon is suggestive of Cottrell&apos;s solute atom atmosphere theory and five points of qualitative agreement with this theory are found. PLASTICITY of germanium at elevated temperatures has been reported by Gallagher,&apos; who ascribed it to slip on {Ill) planes and described some associated effects. Preliminary experiments with single crystals of silicon and germanium loaded as simple beams confirmed {ill) as the slip plane of both materials.V his was demonstrated by the standard technique employing traces on two surfaces of known angle on a deformed crystal of known orientation.3 These experiments did not fix the slip direction, since more than one glide system operated. Uniaxial tensile straining is preferred for this purpose in order to restrict slip to one predominant system and to provide an unequivocal determination of the orientation change with respect to the stress axis. Experimental Method Specimens were diamond-sawed from germanium crystals containing about 5x10-5 wt pct Sb prepared by the zone-leveling process described by Pfann and Olsen;4 these specimens measured about 81/2 in. long, 0.20 in. wide, and were of various thicknesses from 0.035 to 0.060 in. Prior to testing, a specimen was coated over 1 in. or more of length at each end with Apiezon wax, chemically polished (in a solution of 15 ml HF, 25 ml HNO,, 15 ml CH3COOH, and 3 to 4 drops Br2), and dewaxed in warm xylene. A brief re-etching after scribing through a complete wax coating with vernier dividers provided gage marks at 0.200 in. intervals on the polished surface. A specimen with grips soft soldered to the ends was passed through the furnace tube and the grips pinned to the tensile machine in series with a stress gage. The Schopper testing machine is best described by reference to the illustration on p. 107 of Schmid and Boas5 and is operated with the pendulum arm locked, fixing the upper head. Load is applied through the screw-driven lower head, manually or by reduced speed motor. The furnace is 21/2 in. long surrounding a 4x7/16 in. ID quartz tube and was positioned about the specimen to permit free motion. The inert or reducing atmosphere required was sufficiently provided by a flow of helium introduced at the center of the furnace tube, with the tube ends loosely plugged with asbestos paper. Surface corrosion was slight. The stress gage employs a Be-Cu strip with SR-4 units incorporated in a simple bridge network with provision for balancing and calibrating. The bridge output on loading is fed through a Leeds and North-rup dc amplifier to a Speedomax 10 mv recorder, and calibration is obtained by dead loading. Experiments of two types have been conducted. Most have been in relaxation at constant elongation. One stress-strain curve has been taken with the machine continuously driven. Following extension of a specimen, Laue X-ray photographs were taken to obtain the orientation change between deformed and undeformed regions, recorded on a single film by translating the specimen in a plane normal to the beam between exposures. Sequences of such multiple exposures were made on some specimens to include the entire orientation range on one film. Slip Direction To obtain a maximum orientation change with a single slip system, crystals of very closely <110> axial orientation were used. The classic determination of slip direction rests on establishing that direc-

Jan 1, 1956

By J. PARKCEH CHANNING

Discussion of the paper of Lewis T. Wright, presented at the New Haven meeting, February, 1909 (Trans., xl., 492 to 495). J. PARKE CHANNING, New York, N. Y. (communication to the Secretary*):-Mr. Wright, in his introductory paragraph, says: " It is commonly believed by metallurgists that in copper-smelting, the copper in the slags, which is irreducible by continued smelting, is retained in the form of &apos;prills&apos; of matte." On a recent visit to Greenwood, B. C., I was discussing with J. E. McAllister, the general manager of the British Columbia Copper Co., and the former metallurgist of the Tennessee Copper Co., this very question; and he held strongly to the idea that the copper in slag was in two forms-one portion contained in occluded matte and the other as an oxide. He believed that this same rule would apply to the silver in the slag. From my experience I am strongly inclined to agree with Mr. McAllister; and it appears quite reasonable that in furnaces treating oxidized copper-ores, and to a less degree in furnaces treating sulphide ores, there is always bound to be present a certain amount of copper oxide and silver oxide, which will behave like any base and get into the slag as such. We all know that in Arizona, in the early days, when it was customary to produce black copper, because the ores were nearly all oxidized or carbonates, and sulphur was scarce, the slags as a rule carried 2.5 per cent. of copper and seldom ran less than 1.5 per cent. of copper. The economic point was determined by the extra coke necessary to produce the reducing action. In connection with the extra saving in copper, Arthur L. Walker, now professor of metallurgy at Columbia University, and formerly general manager of the Old Dominion Copper Mining Co., at Globe, told me that with coke at $60 per ton it never paid him to make slags containing less than 2.5 per cent. of copper. *Received Oct. 8, 1909.

Feb 1, 1911

By Herbert W. Graham

IRON ORE is widely distributed throughout the world. Ores sufficiently high in iron content to be practical for the operations of iron and steel making occur in so many places that it is only by the accident of political subdivisions that any given nation does not have adequate and suitable iron ore. Data prepared by various authorities show that in the Lake Superior region alone there are reserves of 1,200,000,000 tons of iron ore of an iron content and at the level of production cost to which the industry has been accus tomed. At an annual consumption of 80,000,000 tons these reserves will last fifteen years. Taken alone these figures would be alarming, but over a considerable period of years the total reserve tonnage has been more or less steadily increased by improvement and extension of mining and beneficiation methods. The rate of depletion of reserves has been only about one third of the rate of consumption. On this basis the cheap high-grade ores of Lake Superior would last 45 years.

Jan 1, 1947

By T. S. Fuller

MUCH study has been given by engineers in general, and investigators in particular, to the concentration of stress which occurs under load in structural members having irregularities in section such as notches, shoulders, key ways, tool marks, etc. The result of the effect of both fresh and salt water corrosion upon the endurance properties of various metals and alloys has been ably determined and the general laws underlying these phenomena carefully pointed out by McAdam. From a practical standpoint, &apos;however, it is after all the endurance value of corroded, non-symmetrical sections which is most pertinent. In the experiments about to be described rotating cantilever specimens of nickel steel of the 3.5 per cent nickel &apos; 0.35 per cent carbon type have been used. These were machined from bars l 1/8. in. dia. and 9% in. long and were heat-treated by quenching in oil from 825 deg. C. followed by reheating to 650&apos; C. and oil quenching. The tensile and impact properties of this material so heat- treated follow:

Jan 1, 1931

By Lucius W. Mayer

The iron-mines of the Ilsede Hütte Co. are at a town called Peine, about 20 miles east of the city of Hanover, on the railroad to Brunswick (Braunschweig). Hanover, the capital of the province, is a military city, of approximately 250,000 inhabitants, and Brunswick, 33 miles to the westward, has half this number. The mines here described are located in a hamlet called Bülten. The Ilsede Hütte Co. operates two mines, 1.5 miles apart, in this district, Gruber Bülten Adenstadt and Gruber Lengede Bodenstadt. It also operates an iron-mine north of Hanover, known as Eiserhaven, and one in the Harz mountains, the Georg Friedrich, at Grauhof. At Bülten a coarse conglomerate, a, Figs. 1 and 2, contains nodules of limonite, cemented together by calcium phosphate. The ore contains Fe, 25 to 45; Mn, 3 to 4; P, 0.6 to 1.4; S, 0.02 to 0.09; and CaCO3, 40 per cent. Directly above the conglomerate is limestone, b, followed by a mixture of clay and sand, c. Below the conglomerate is a hard clay floor, d. The ore-body, from 10 to, 12 km. long, and from 3 to 4 km. wide, has a maximum thickness of 20 m. It clips approximately 10° S.E., and strikes N. 45° E. Diamond-drill prospecting shows that the thickness diminishes to 1 m. as the end of the deposit is approached to the northward. At this point the deposit is 250 m. below the surface. In Fig. 2, the arrow, A, indicates the general direction of the work along the face, a, which is carried forward in a straight line for its entire length. At B, a train is approaching, which has come from the bench-track, shown at G, by a circuitous route, and is dumping the overburden behind the face, in the space left by the excavated rock. Formerly the work at this mine was essentially open-cut, the deposit having a very strong outcrop. Figs. 1 and 2 show also

Sep 1, 1908

By Thomas A. Lang, John A. Bischoff

The use of rock bolts for the support and stabilization of coal mining excavations was introduced over 30 years ago and, since that time, has progressively increased until today it is the primary means of support and stabilization of large underground openings. Early analytical studies and work with photoelastic and physical models established that even highly fragmented rock could be stabilized by rock bolting and form a load-carrying structural member that would span an opening. For stability, interaction of the bolts is essential and it depends on the bolt tension, the length and spacing of the bolts, the characteristics of the rock, and the applied load. However, the development of an explicit functional relationship embracing all these factors proved to be elusive. A review of the early rock bolting investigations led to the concept that the basic element of a rock bolted roof is the reinforced rock unit (RRU), consisting of an individual bolt and the rock immediately surrounding and adjacent to it, and to the development of mathematical equations which give the minimum bolt tension required to ensure that the RRU&apos;s are stable relative to one another and act together as a structural member. Analytical procedures have been developed for integrating RRU&apos;s into a reinforced rock structural (beam-arch) member which spans an underground opening and providing a rational basis for the design and installation of rock reinforcement systems.

Jan 1, 1982

By A. U. Seybolt

A. U. Seybolt (General Electric Research Laboratory)— As pointed out in an earlier paper,41 it appears to be very difficult to nucleate Si3N4 in Si-Fe of silicon content up to around 5 pet. Therefore, one observes, as did Pearce, that equilibrations with nitrogen gas yield only nitrogen in solid solution at temperatures above about 700°C, or, as Pearce found, 770°C. Evidently, the free energy of formation of Si3N4 only becomes high enough at -770°C to overcome the reluctance of Si3N4 to nucleate. However, as mentioned in Ref. 41, if some Si3N4 is first formed by a mixture of ammonia and hydrogen, one can then replace this gas mixture by nitrogen gas, and either increase or decrease the amount of Si3N4 present at any temperature by suitable adjustment of nitrogen pressure: that is, to equilibrate with Si3N4. In the equilibration experiments cited in Ref. 41, equilibrium was approached from both sides, and it was found that samples up to 944oC, at least, were in equilibrium with Si3N4. Higher temperatures were not employed, as this would have necessitated a redesign of the apparatus for using nitrogen pressures in excess of 1 atm. To summarize, the results of Pearce&apos;s experiments and those of Ref. 41 cannot be directly compared because two quite different equilibria were studied. Therefore, the statement by Pearce on p. 1398 indicating apparent error in Ref. 41 is unjustified. M. L. Pearce (author&apos;s reply)— There was limited evidence obtained in the current investigation which would indicate that excessive "supercooling" did not occur. A small piece of the same resulting from heat treatment No. 5 in Table III was subsequently held at 800°C for 16 hr in 95 pet N-5 pet H. Isotope-

Jan 1, 1964

By W. D. B. Motter

DURING the early development of blasting with liquid oxygen explosives the trend of experimentation was towards increasing the effectiveness of the explosive. Its characteristic of becoming inert after evaporation of the oxygen content made a strong appeal from the standpoint of safety, especially with missed holes. It later became apparent, however, with practical use of this explosive, that LOX lacked certain other safety characteristics. As its effectiveness was increased, it became more subject to detonation by impact. The object of this paper is to show the steps taken by one operating company to achieve greater safety in the large-scale handling of liquid oxygen explosives.

Jan 1, 1933

By WALTER B. JONES

PIG iron was first produced in Alabama in 1818 from limonite or brown ore and since then much of this ore has come from the so-called mineral district of northern Alabama, especially along the Cretaceous-Paleozoic contact. For many years the Russellville district in Franklin County, where the first blast furnace was erected, produced more than 100,000 tons of brown ore annually. Limonite has been reported at many places in the Coastal Plain region, where the formations are of Mesozoic and Cenozoic age, but these scattered deposits were never considered to be of much commercial importance. However, in the last three years a considerable quantity of this ore has been scraped up and shipped, particularly from the city of Greenville in Butler County.

Jan 1, 1938

By David L. Holt

The contribution of grain boundary shear to total elongation, CS/E&apos;, has been measured in an Al-Zn eu-tectoid alloy that was quenched from above the invariant temperature, then annealed at 250° C to a grain size of&apos; 1.8 p. At 250°C, ks/E&apos; is low at both high and low strain rates, but reaches a maximum, estimated as 60 pct at an intermediate rate of 5 X 10 per rnin. Rate sensitivity, as measured by the index m = a log a/a log E&apos;, follows the same trend, and furthermore the maximum values of m and -cur at approximately the same strain rate. This result, combined with the metallographic observation that boundary migration enhances boundary shearing, is interpreted as supporting a previous suggestion that the high rate sensitivity characterizing super-plasticity is the result of combined boundary shearing and migration. It is suggested that the latter event relieves stress concentrations at triple points, and smoothes boundaries so that stress is governed largely by a viscous boundary shear. GrAIN boundary shear has been considered in relation to superplasticity in several recent papers.&apos; The problem has been to explain the high strain rate sensitivity of flow stress, and the variation of rate sensitivity with strain rate (E&apos;) and grain size (L). The requirements for superplasticity, small L and high T, suggest the reasonableness of an approach to high rate sensitivity involving grain boundary shear. Further support came from experiments on the A1-Cu eutectic alloy,&apos; where it was found that strain rate sensitivity of cast material annealed to produce an equiaxed, micron-size grain is always low; taking as an index of rate sensitivity m = a log a/a log <, m < 0.3. However, m in hot-worked alloy of comparable grain size can be as high as 0.7. In the cast and annealed material, each phase is a single crystal, the only boundaries are interphase boundaries, and it is, consequently, geometrically impossible for boundary shear to contribute to deformation in any major way. Other observations (for hot-worked material) were a-L at constant (low) strain rates and indications that the rate of recrystallization was enhanced as strain rate increased. As a result of this work, it was proposed that high rate sensitivity arises from a deformation mode of boundary shear associated with boundary migration. Migration serves to relieve stress concentrations at triple points, and smoothes boundaries so that they assume properties of fluid films. On the other hand, the low rate sensitivity observed at high and low strain rates reflects deformation of bulk material. Measurement of the variation of grain boundary shear with strain rate and m have not yet been made. Such measurements are important, especially in view of a proposal, differing in detail from the above, that high m arises merely from a transition between a grain boundary shear mode of deformation at low rates to a transgranular mode at high rates.2&apos;4 In the present work, the contribution of boundary shear to total deformation is measured and in addition metallographic observations are made on surfaces of deformed specimens to look at the interaction between boundary shear and migration. The Al-Zn eutectoid alloy was chosen for its homogeneous, fine-grained structure, which is obtained readily without hot-working. It has also been the subject of a previous phenom-enologically directed study. EXPERIMENTAL Material. Compression specimens, cross section 4 by + in., length \ in., were machined from a sand-cast ingot of composition 77.5 wt pct Zn, 22.5 wt pct Al. (The melt was prepared from 99.9 pct Zn and 99.99 pct Al.) After homogenization at 375°C for 50 hr, the specimens were quenched in brine and removed before the heat evolution that accompanies de -composition of the high-temperature phase.5&apos;6 The resulting microstructure, see Fig. l(a), was too fine for grain boundary sliding to be easily studied; coarser structures were obtained by annealing for various times at 2 50°C. Annealing was terminated by a brine quench. Final average intercept lengths between all grain boundaries (both interphase and those lying in a phase), L, were: 0.5 p [annealed for 15 min, Fig. (a)], 0.8, 1.1, and 1.8 p [Fig. l(b)l. Testing Procedure. An Instron machine was used for most of the compressive deformation. Tests were of two types: those in which crosshead velocity was changed in steps to measure m as a function of strain rate15 and tests at constant velocity to a fixed (engineering) strain of -0.2 (20 pct). Stress reached a steady-state value (a) which was plotted, on a logarithmic scale, against log strain rate (E&apos;). An alternate and equivalent evaluation of m was to take the slope of the log o vs log 6 curve. Time at temperature before testing was 15 min. Strain rates covered by the Instron (4 x lo-&apos; to 4 x 10&apos; per min) were insufficient; at a higher rate of 5 x lo2 per min a gas-operated testing machine was used, the gas driving a piston to compress the specimen at a controlled velocity.&apos; To obtain points on the log a vs log E&apos; curve at low rates, specimens were compressed by a dead weight. strain rate was an average value computed by dividing strain at the end of test by loading time. In some tests strain was measured at fractions of the loading time; creep rate was found to be reasonably constant.

Jan 1, 1969

By C. W. Dunham

DESIGN of the structures for the Morenci Reduction Works involved many interesting problems. Naturally, the chief purpose of these structures is to house and support the equipment and other things necessary for or incidental to the conduct of production. hence most of the features of the design were developed to suit these particular conditions; however, several are so generally applicable as to warrant description.

Jan 1, 1942

Jan 1, 1884

By W. J., Kroll

MOST people believe that rare metals are always, scarce in nature, expensive to make, and therefore useless despite some miraculous properties which might make them a cure-all. There are&apos; some metals, which are quite frequent in nature, such as zirconium, which are called rare only because our present methods for making them are elaborate, thus forcing the manufacturer to sell them at a high price. There are also truly rare metals, such as gallium, which do not occur frequently in ores, but are easily reducible from their oxides. In these cases the price of the concentration operation is the decisive factor. The distribution of the elements in the earth&apos;s crust is no indication as to the availability of a metal; the concentration operation is the critical factor. Concentration is frequently obtained in the course of metallurgical operations for the extraction of other metals, and the rare metal may be enriched in by-products, flue dusts, mother liquors or precipitates from electrolyte purification as are indium, thallium, selenium, and tellurium. A periodic table of the rare elements may serve as a basis for discussion of their properties and to establish a program. (Table 1.)

Jan 1, 1946

By J. J. Gilman

THEORIES of fracture in metals have been based primarily on the dependence of fracture strength on grain size. This dependence was first observed by Masing and Polanyi.l These workers, as well as 0rowan12 and Davidenkov and Wittman,&apos; thought the grain size could be equated with the crack size in the Griffith condition for crack propagation.4 In this way they could account for the observed proportionality between fracture stress and the reciprocal square root of the grain size. The chief results of recent investigations of the fracture strength of polycrystals are summarized in Fig. 1. Low for iron,5 Petch for iron,&apos; Greenwood and Quarrel for zinc, Petch and Zein for zinc,&apos; and Hauser, Landon, and Dorn for magnesium&apos;&apos; have all found that the fracture stress of a polycrystal is proportional to the reciprocal square root of the grain size. Also, they find that, for large grain sizes, the fracture stress lies near the extrapolation of the yield-stress curve determined at small grain sizes; where measurable plastic strain precedes fracture. Low9 has gone a step further and shown that, in Range 1, the fracture stress in tension is almost identical to the yield stress in compression for a given grain size. Homes and Gouzou, 10 and Low also have shown that, in Range 2 of Fig. 1, microcracks form when the yield stress is reached, but they do not cause failure until the stress reaches a much higher value. The fact that yielding always precedes fracture suggests that fracture is induced by plastic flow. A mechanism by which this might occur was first proposed by Zener.11 He pointed out that blocked dislocations would cause stress concentrations which might cause fracture. The blocking would be caused by grain boundaries. This idea has been developed by Eshelby, Frank, and Nabarro,12 by Koehler,13 and by Stroh.14 By means of etchpits blocked dislocations have been observed in brass by Jacquet,15 in zinc by Gilman,16 and in lithium fluoride by Gilman and johnston. The blocked-dislocation theory and the experiments that bear on it have been summarized by Mott.18 One of the strong points of the blocked-dislocation theory is that it can explain the grain-size dependence of the fracture stress in a natural way. However, Low9 has pointed out that the theory is not satisfying when it is considered quantitatively. Gilman10 also has criticized the theory and presented an alternative interpretation of the relation between fracture stress and grain size. Since the blocked-dislocation theory is not the only theory that can explain in the grain-size effect, it is necessary to find other evidence either to support or deny it. In this investigation the following points were studied: 1) If blocked dislocations normally cause fracture, then the fracture stress ought to be very high in the absence of plastic glide. Is it? 2) If dislocations must be blocked in order for metals to fracture, then certain types of grain

Jan 1, 1959

By F. M. Stewart

A paper by Hurst and van Ever-dingen in 1949 led to the practical solution of many nonsteady-state flow problems.&apos; Subsequently, applications of this material have been discussed by several authors. The purpose of this note is to outline a simplified direct procedure for water-influx pressure predictions for pressures above the bubble point. The prcposed procedure is unique in that after the "time-conversion factor" and the "influx constant" are obtained, predictions are made without trial and error. The elimination of trial and error is made possible by expressing certain PVT characteristics as explicit functions of pressure. The procedure is applicable to fields producing at pressures above the bubble point and under radial water drive from an infinite aquifer. In the usual applications it is required to predict (1) withdrawals given future pressure history or (2) reservoir pressure, given future withdrawals or production. The theory, assumptions and conditions under which the nonsteady-state solutions hold are covered in the references and are not repeated. The simplified direct procedure outlined here has been developed from published solutions for the so-called "pressure case". A similar direct procedure for the same special conditions has been developed for the "rate case"; however, in this instance the procedure is lengthy and offers no advantage over the trial-and-error solution. Consequently, this paper covers only the procedure based on the pressure case. DISCUSSION Under the pressure case prediction of withdrawals from a water-drive field, given the future pressure history, involves the use of a nonsteady-state water-influx term together with the material balance equation. The solution of a particular problem requires the following steps: (1) division of past pressure and production data into equal time intervals; (2) computation of cumulative water influx vs pressure drop for each time interval of past history using the material balance equation; (3) determination of the best values for the "time-conversion factor" and the "influx constant" by equating the nonsteady-state influx term with the influx computed in Step 2 (this requires a trial-and-error procedure); (4) prediction of influx for a given pressure drop using the influx term and the computed factors from Step 3; and (5) calculation of fluids produced using the predicted influx in the material balance equation. A forecast of the water-oil ratio or water production rate is required to complete the calculation. It is assumed that a reliable estimate of original oil in place is available, as well as the production and pressure history, and data on reservoir fluid characteristics. If the original oil in place is unknown, it may be computed simultaneously with the tinie-conversion influx factors2,3. However, the oil in place so computed may be considerably in error3; consequently, it is usually preferable to use oil in place estimated from pore-volume data unless there is considerable doubt as to its accuracy. The Material Balance Equation Above the Bubble Point Above the bubble point the simpli-

By Irwin H. Cornell

BRIEFLY stated, the history of the St. Joseph Lead Co. is the story of how a group of men, working for ten years as officers without salaries and stockholders without dividends, developed a small mine in Missouri into what became a large and prosperous corporation. Their courage and faith in the scattered surface deposits of lead coupled with the management&apos;s engineering vision and sound financial judgment should prove an inspiration to present-day mining operators and investors. In 1717, John Law&apos;s company, known as "The Company of the West," was formed in France and letters patent were granted, for a period of 25 years by Louis XV, for exploration in the Mississippi River Valley. One of the underlying purposes of the expedition, headed by Mr. Renault and Mr. La Motte, a French metallurgist, was development of the lead mines in the area now known as Southeast Missouri.

Jan 1, 1947

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman&apos; have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956