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By J. A. Goebel, S. Rosen

IN the NiAl phase diagram the NiAl (CsC1-type) phase field extends over a large composition range. At elevated temperatures the nickel-rich phase boundary extends to a composition of about 70 at. pct Ni, a value which is within 5 at. pct of the Ni3A1 (Cu 3 Au-type) phase boundary.' At room temperature, however, the maximum nickel content is only about 60 at. pct. Experiments have shown that alloys containing greater than 63 at. pct Ni when quenched from temperatures below 1000°C contain the equilibrium phases NiAl and Ni3A1. On the other hand, when these same alloys are quenched from temperatures above 1000°C and examined microscopically, a typically martensitic decomposition product appears in the microstructure as shown in the micrograph of Fig. 1. The structure of the martensitic phase has been determined by employing powder X-ray diffraction techniques to be an "ordered" AuCu type (Strukturbericht Llo, space group P/4 mmm - DL). The diffraction pattern of this phase differs from that of AuCu in the appearance of superlattice lines. The structure is shown in Fig. 2. The open circles represent nickel atoms and the half-shaded circles represent nickel and aluminum atoms which are randomly distributed. The sites represented by half-shaded circles would be occupied solely by nickel atoms at a stoichiometry of Ni3A1. The alloys used in this investigation were prepared from 99.99 wt pct Al and 99.99 wt pct Ni by arc melting charges of varying compositions in a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. In all cases chemical analysis agreed within $ at. pct with the nominal compositions of the alloys. Annealing treatments were carried out in a vertical resistance furnace through which a stream of argon gas was flowing. Specimens, which were wrapped in tantalum foil, were quenched by allowing the specimens to drop into a bucket containing iced brine. X-ray diffraction patterns were obtained from -325 mesh powder specimens by using a 114.8-mm

Jan 1, 1969

By D. Weinstein

The high temperature mechanical properties of stainless steels after fast neutron irradiation are discussed in the light of effects caused by lattice dattmage and effects caused by helium generated from n,a transmutations. Embrittlement at high temperatures is due to helium accumulation at grain boundaries and to cavity formation and proPagation along grain boundaries. Following from the embrittlement mechanism, it is suggested that when deformation occurs by mechanisms associated with super plasticity, helium ac-curnulation at boundaries should be attenuated and cavities, if formed, should be nonpropagating. As the mean free Path between interphase boundaries of a two-phase Fe-Cr-Ni alloy was decreased, the degree of superplastic deforrnation at 870°C increased, as vneaszired by total elongation and by the expottent m = a log 'a/a log 'i. This alloy and type 304 stainless steel were cyclotron irradiated in an a-particle beam to a helium concentration of -1 x 10 atom He per atom. The stainless steel specimen was embrittled, but the ductility of irradiated two-phase Fe-Cr-Ni alloys correlated with the values of. m during 'defor-malion. The .finest grained, helium-injected specimens that deforrned with highest m values exhibited the largest elongations to ,fracture. These results could be correlated with metallographic observations of cavity behavior: the propensity for intergranular propagation was lessened as the m value increased. It is concluded that superplastic deformation is ef-fectizle in attenuating helium embrittlement at elevated temperatures. One of the principal problems associated with development of fast breeder reactors is application of alloys such that suitable fuel cladding results. Stainless steels and other Fe-Cr-Ni alloys, because of highly acceptable nuclear characteristics, represent the primary materials for this component, and an exhaustive research and development effort is being conducted. The main deficiency of these materials has been a severe loss of ductility at high temperatures after fast neutron irradiation. An extensive body of mechanical property data and microstructural observations has provided an adequate phenomenological description of embrittlement; in conjunction with transmission electron microscopy studies, a reasonably acceptable embrittlement mechanism has been obtained. Following from this mechanism, it is suggested in the present work that ductility would be enhanced if deformation could occur by mechanisms associated with the phenomenon of superplasticity. Experiments to test this hypothesis have been conducted, and the results are presented and discussed in this paper. IRRADIATION EMBRITTLEMENT AT HIGH TEMPERATURE Austenitic stainless steels have been irradiated to accumulated fast neutron fluences of 1020 to 1022 nvt at temperatures between 60" and 600°C. Specimens that have been exposed to these conditions and subsequently tensile tested at temperatures between 600" and about 900°C exhibit approximately 5 pct total elongation to fracture.'-3 For unirradiated specimens receiving a nearly identical thermal exposure, total elongation at these test temperatures is about 45 pct. Examination of irradiated specimens has shown that fracture propagation is entirely intergranular. These phenomenological aspects of irradiation embrittle-ment at elevated temperatures are well known and are not generally disputed. Although the explanation of this phenomenon has been controversial, a mechanism for ernbrittlement has emerged that accounts reasonably well for the observed mechanical behavior. The controversy resulted primarily from an indeterminate role of neutron-in-duced lattice damage, if any, and a presumed, but experimentally unverified, contribution to embrittle-ment from helium generated by n,a transmutations. Recently, Holmes and coworkers4 have conducted experiments that separate these effects, and the results are instructive in formulation of the ernbrittlement mechanism. Holmes el al.4 irradiated type 304 stainless steel in EBR-I1 to a fluence of 1.4 x 1022 nvt (E > 0.18 mev); the irradiation temperature was 538" * 48°C or, in terms of absolute melting point, 0.49 * 0.03 T,. After irradiation, tensile tests were conducted at temperatures of 21" to 870.C, the specimens first being annealed for 30 min at each test temperature. In addition, thin sections of irradiated specimens were annealed for 1 hr at identical temperatures, electro and examined by transmission electron microscopy. Thus, for a given temperature, it was possible to correlate mechanical properties with the defect structure. At room temperature, the yield stress of irradiated specimens was a factor of 2.5 higher than unirradi-ated specimens exposed to an equivalent thermal history. Electron microscopic examination of the irradiated specimen revealed a high density of lattice damage in the form of Frank sessile dislocation loops and polyhedral voids. Holmes et al.4 concluded that the presence of this defect substructure caused the increase in yield stress and that after irradiation in a fast neutron flux at 0.49 Tm, substantial lattice dam-age persists. Annealing at progressively higher tem-

Jan 1, 1970

By James B. Cathcart

Marine phosphorite deposits occur in Braxil, in the Bambui Group of late Precambrian or Early Cambrian age. The phosphorite is laminated, isoclinally folded, and is composed of black, elongated apatite pellets and quartz grains cemented by quartz and muscovite. Abundant, narrow quartz veinlets cut through the .rock at right angles to the elongation direction of the pellets. The phosphorite is 0 to 80 m thick and contains 5 to 30 percent P2O5. The deposit is elongate towards the northeast, and the central, thickest, and richest part is bounded by faults. Measured reserves are about 250 million tons that average a bout 13 % P205. Preliminary testing indicates that grinding, scrubbing, and desliming will produce a material usable for fertilizer manufacture at a cost competitive with imported phosphate fertilizers.

Jan 1, 1979

Albin, B. R Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, 111. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. '28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. '28 Benwell, Oswald F Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1936

By Takahide Wakamatsu, Douglas W. Fuerstenau

Contact angles on alumina are related directly to the adsorption of alkyl sulfonates at the solid-water interface and thus are strongly controlled by the pH of the solution, the concentration of surfactant, and the number of carbon atoms in the alkyl chain. As the pH of the solution is increased above the point of zero charge, sulfonate adsorption ceases and alumina remains hydrophilic. However, in neutral and acidic solutions, contact angles increase markedly in magnitude when the adsorbed sulfonate ions form hemimicelles at the solid-water interface. Under a wide variety of solution conditions, a limiting value of the contact angle is attained at the point of reversal of the zeta potential. Finally, contact angle phenomena are empirically correlated with the sulfonate adsorption density through the work of adhesion.

Jan 1, 1974

Albin, B. R Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, 111. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. '28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. '28 Benwell, Oswald F Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1934

Herewith are transmitted the joint report of the Treasurer and Finance Committee for 1934 and the reports for the same year of the Chairmen of the following Committees: Admissions, Membership, Papers and Publications, Library, and MINING AND METALLURGY. TO these reports you are referred for details of the year's activities. Finances.-Income for 1934 from all sources totalled $134,967 com- pared with $121,689 in 1933. The increase is accounted for principally by four items: $6000 increase in initiation fees and dues of new members; $1800 in current dues; $4000 in "back" dues; and $2800 in the sale of publications, including TRANSACTIONS volumes and technical papers in the form of "separates." In passing, it may be remarked that income from back dues during 1935 will be less than in 1934, for the obvious reason that the total amount of dues in arrears has shrunk and consequently there is less to draw from. Income from

Jan 1, 1934

By John W. Langley

In the summer of 1888 it was the fortune of the writer to present the subject of the desirability of establishing a set of samples of steel, which should be analyzed with extreme care, in order that they might become standards to which scientific and commercial analyses of iron and steel could be subsequently referred; also, that greater uniformity in the results of analyses might be brought about, since these standards would bear towards analytical methods somewhat the position which the original units of weight and length, the gramme and meter, or the pound and yard, preserved in Paris, London, and Washington, do to the mechanical arts. The plan met with hearty co-operation, with the result that com mittees were appointed in Sweden, Germany, France, England, and America, to receive the material and to see that the necessary au alyses were executed. In England, the British Association for the Advancement of Science appointed a committee, which subsequently published a plan

Jan 1, 1891

By E. Peters

As in other fields of Extractive Metallurgy, Hydrometallurgy is preoccupied with separation processes and with oxidation-reduction processes. The physical chemistry of each type of process can be described in terms of thermodynamic equilibria and in terms of reaction kinetics. Reaction kinetics are much more important at the low temperatures limiting hydrometallurgical processes than in com- parable pyrometallurgical operations and the number of cases in which the kinetics can be described by simple liquid-phase mass-transfer models are sharply limited. It is convenient to subdivide the applicable rate phenomena into processes in which (a) interface reactions control the rate,(b) mass transfer processes control the rate, (c) solid state process affect the rate, (d) thermodynamically predicted phase changes or molecular reactions fail to take place, (d) metastable substances or supersaturated phases persist, and (elchomogeneous reactions in solution affect the chemistry and the kinetics. Examples are drawn from the unit steps of leaching, cementation, hydrogen reduction, and electrowinning.

Jan 1, 1973

By H. W. Schadler

The superplastic behavior of low carbon and manganese bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests are reported which indicate that high strain rate sensitivity (>0.5) and adequate elongations are achievable in ultrafine-grained steels 1 to 2 p, but at strain rates which are not commercially attractive. It has been demonstrated that the fine grain size is retained after long times and high strains if the temperature is kept within the range of the two-phase (a + ?) field. INTEREST in superplasticity has been stimulated by the desire to: 1) understand the origin of, and mechanisms responsible for, the large uniform elongations observed, and 2) exploit this property for commercial advantage in metal forming operations. Although the Zn-22 wt pct Al alloy presently being studied as a model material1-5 may find application in sheet forming and extrusion, the potential of super-plasticity should best be realized in large tonnage materials, such as steel and aluminum alloys. The degree of superplasticity in low-carbon and manganese-bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests on ultrafine grain size material are reported. Avery and Backofen6 and Hart7 have shown that geometrically stable flow leading to extensive uniform elongation in the tension test is associated with high values of the strain rate sensitivity, m, defined: Lozinsky had reported that titanium and zirconium experience permanent deformation if subjected to a constant load and cyclic heating through the temperature range of the phase transformation. Although strain rate sensitivities in excess of about 0.2 had not been reported previously for steel, permanent deformation had been observed11-13 in a wide variety of steels subjected to a constant load and cyclic heating through the temperature range of the a-? phase transformation. Thus by analogy, steel could be expected to exhibit high strain rate sensitivity but only in the a + ? condition. High strain rate sensitivity has been observed at 650°C (a + Fe3C), but not reported as such, by Bailey, Dickenson, and pearson14 in 1931 at a strain rate of about 10-9 per min. It then remained to determine whether high tensile elongations would be observed in a rate-controlled test at constant temperature and at what strain rate strain rate sensitivity values greater than 0.5 would be observed. Since previous experience8 had indicated the importance of fine grain size to realizing high m at reasonable strain rates, it was first necessary to produce an ultrafine grain size and then keep the grains from growing during the test. The results of this investigation show that fine grain size can be readily produced16 and maintained by restricting the temperature of testing to below the ? transus. Further, superplasticity (high m and large uniform elongation) is observed. However, the strain rate range is only marginally useful for commercial forming operations with the finest grain size produced. MATERIAL The material investigated initially was a 1.9 wt pct Mn, 0.42 wt pct C, hot-rolled bar previously used by Low and Turka1015 and available in the laboratory. The 0.500-in. round was cold-rolled to a 0.090-in. flat, annealed for 4 hr at 850°C in argon, air-cooled, and cold-finished to 0.050 in. Subsequently, four additional steels of the compositions given in Table I were investigated to explore the effects of manganese, carbon, and test temperature on the observed stress-strain rate behavior. These steels were melted under argon, cast to 0.75 by 2 by 5 in. slabs, hot-rolled at 850°C, surface-finished to 0.13 in., and cold-finished to 0.050 in. Sheet tensile specimens 0.200 in. x thickness with 1- or 2-in. gage length were cut parallel to the rolling direction. Table I also includes the nominal transformation temperatures for the AISI 1340 and the four experimental steels. EXPERIMENTAL PROCEDURE Production of Fine Grain Size. Ultrafine grain size (1 to 5 p) was considered essential for this studv. Grange16 has described two techniques for producing

Jan 1, 1969

By J. F. Abel, F. T. Lee

Subsidence is controlled by a complex com¬bination of mining and geologic factors. For example, a compilation of worldwide data shows that, as the percentage of shale in the overlying rock mass decreases and the amount of sandstone increases, the angle of draw (and the area affected by subsidence) decreases. Limestone in the over¬burden appears to cause a more than twofold decrease in the angle of draw compared to a like amount of sandstone. Increased amounts of sandstone were accompanied by a greater surface subsidence relative to the mining height. The total thickness of overburden did not appear to influence the subsidence magnitude above super-critical panels. The greater the thickness extracted, the smaller percentage of that thickness shows up at the surface as subsidence. The greater the percent of the seam extracted, the greater the subsidence reaching the surface. The maximum subsidence above room-and-pillar panels de¬pends on the pillar height and minimum width as well as the other factors listed.

Jan 1, 1984

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.' on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-' (g S per sq cm)' corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.' The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969

THE CHAIRMAN (F. K. COPELAND,* Chicago, Ill.).-At this particular time conditions existing in this, country, and elsewhere, make all questions of milling or smelting or mining, or anything else, absolutely secondary to the one question of labor. We have always devoted our attention largely to the efficiency of machinery, and to reductions in costs, etc., and have let this tremendous problem of our relation to labor more or less take its own chances. There has never been a time when those who are responsible for the operation of business of different kinds were as com-pletely at a loss as they are now, so that anything that can be brought out that relates to labor is, to my mind, of utmost importance. T. T. READ, Washington, D. C.-This formulation of a method of curtailing forces at the Copper Queen is a notable step in advance of our treatment of personnel in the mining industry. So far as I know, it is the

Jan 12, 1919

Executive Committee, Board of Directors Augustus B Kinzel, Chairman, J L Glllson, Vice-Chairman, A W Thornton, Howard C Pyle, Grover J Holt Finance Committee, Board of Directors Andrew Fletcher, Chairman, J S Vanick, Gall F Moulton Investments Gail F Moulton, '60, Chairman, Henry Krumb, '59, J Loveloy, '61, C R Dodson, ex off as Treasurer, Andrew Fletcher, ex off as Chairman, Finance Com¬mittee Endowment Andrew Fletcher, Chairman, N G Alford, H DeWitt Smith, W J Coulter, J V N Dorr, R B Gilmore, J B Haffner, O H Johnson, D H McLaughlin, J R McMillan, L F Reinartz, C E Weed, Wilfred Sykes, J R Suman Honorary Memberships H DeWitt Smith, '59, Chairman, C E Reistle, Jr, '59, Grover J Holt, '59, L F Reinartz, '59, M L Haider, '60, D H McLaughlin, '61, John M Lovejoy, '62, Augustus B Kinzel, ex off as President

Jan 1, 1958

Jan 1, 1985

By R. T. Hukki

This paper presents a series of equations for mechanical ball wear, relating parameters of ball size, mill speed, and mill diameter. The fundamental equation, Eq. 12, presented here is introduced to correlate these basic parameters and thus define and clarify the concept of ball wear. This equation is offered as a general rule, which may be modified to apply to individual problems of grinding. BALL wear as observed in grinding installations is the combined result of mechanical wear and corrosion. Corrosion should be a linear function of the ball surface available. Ball corrosion, however, has been studied so little that its effect, although of great importance, cannot be included in the analyses given here. In a separate paper' it is shown that 1 n = 0.7663 np----=— rpm [1] vD P = c, np D kw [2] T=c²(np)n De tph [3] In these equations n — actual mill speed, rpm np = calculated percentage critical speed D = ID of mill in feet P = power required to operate a mill, kw T = capacity of a mill, tph C¹ and c² - appropriate constants in = exponent of numerical value of 1 5 m 1.5 Exponent m is the slope of a straight line on logarithmic paper relating mill speed (on the abscissa) and mill capacity (on the ordinate). It is generally accepted, although not sharply defined, that ball wear in mills running at low (cascading) speeds is a function of the ball surface available. Accordingly, the wear of a single ball may be considered to be a homogeneous, linear function of its surface and of the distance traveled. Thus dw = f¹(d2) . f2(ds) [4] where dw is the wear of a single ball in time dt, d the diameter of the average ball in ball charge, and ds the distance traveled by the ball in time dt. Indicating that ds - a D n dt, the wear of the average ball in time dt becomes dw = f¹(d2) . f2(Dn dt) 1 --- f¹ (d1) f² (D c3 np-----— dt) \/D = c,d² n, D dt The rate of wear of the average ball is given by dw/dt. dw/dt = c, d² np D lb per hr [5] The weight of the ball charge per unit of mill length is a function of D The number of balls of size d in the ball charge is = f³(D2)/f4(d³). The rate of wear of the total ball charge equals the number of balls times rate of wear of the average ball. Thus rate of total ball wear = — . (dw/dt) w. c, . (l/d) . n,, D lb per hr [6] which is the equation of ball wear in low speed mills. In a mill running at a low speed, grinding is the result of rubbing action within the ball mass and between the ball mass and mill liners. When the speed of the mill is gradually increased toward the critical, the impacting effect of freely falling balls becomes increasingly prominent in comparison with the rubbing action. Reduction of ore takes place partly by rubbing, partly by impact. The share of the freely falling balls in the reduction of ore reaches its practical maximum at a speed somewhat less than the critical; at that speed grinding by rubbing has decreased to a low value. It may be reasonable to think that size reduction by freely falling balls should reach its theoretical maximum at the critical speed, if the fall of the balls were not hindered by the shell of the mill beyond the top point; grinding by rubbing would cease at the critical speed. As a first approximation, wear of freely falling balls may be considered to be a homogeneous, linear function of the force at which they strike pieces of rock and other balls at the toe of the ball charge. The force equals mass times acceleration. The mass of a ball is a function of d3 and its acceleration is a function of the peripheral speed of the mill. The wear of a single ball of size d representing the average ball in a ball charge will therefore be w¹ = f3(F) = f (d3) f7 (v). [7] Indicating that v = D n, and n = c³ np 1/vD, Eq. 7 becomes W1 = cn d3 np Do.5 lb per hr. [8] Total wear of the ball charge equals number of balls times the wear of the average ball. Number of

Jan 1, 1955

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By N. Mungan

Formation damage, i.e.. reduclion in permeability, has been generally attribuled to clay minerals which expand or disperse upon contact with water that is less saline than the connate water. Luboratory, studies show that penneahility reduction can also occur in formalions containing only nonexpandable clays such as illite or kaolinite, and can be caused also by changes in pH. Furthermore, pH changes can damage even formations that are essentially free of clays. It is suggested that permeability reduction is due to the small passages being blocked by particles, which may be dispersed clays, cemenlion material or other fine parricles. These particles are dislodged by dispersion of clays due to changes in salinity or by dissolution of calcareous cement by acids, or of silicaceous cement by alkaline solutions. In working with reservoir cores, it was found that extracted cores damaged more easily and extensively than nonextracted cores. The extent of damage depended also on tenlperatltre. INTRODUCTION Permeability is an important property of porous media and has been the subject of many studies by engineers and geologists. Many of these studies are conccrned with formation damage, i.e., reduction in permeability, resulting from exposure of oil-producing formations to water substantially less saline than the connate water. This effect causes understandable concern since during drilling, completion and production phases formations are often exposed to fresh water. The damage resulting from contact with relatively fresh water has been attributed to expansion and dispersion oF clay minerals. During laboratory investigation of the use of NaOH as a wettability reversal agent to increase oil recovery from oil-wet reservoirs, several cores used in the displacement studies suffered loss in permeability. Despite the traditional usage of NaOH for conditioning aqueous mud systems, the role of the caustic filtrate in wellbore damage seems to have been overlooked. Browning2 as recently reported on the effects of NaOH in dispersing clay minerals but he was concerned only with complications that may arise in drilling massive shale beds. The following study was made to examine the role of pH and salinity changes in core damage. Where cores from reservoirs were used, tests were performed with extracted and nonextracted cores both at room and reser- voir temperatures, since it was felt that the test environment and core condition may affect the results. Because of its limited coverage and exploratory nature, this study is not intended to provide answers to field formation damage problems. It is hoped that it will encourage research into new aspects of the permeability reduction problems, particularly those allied to new recovery and production processes. PROCEDURE In all permeability tests, fluids were pumped through the cores at a constant volumetric rate. Only deaerated fluids and reagent grade chemicals were used. The fluids were passed through two ultrafine filters before injection to remove any entrained particles. The cores, with the exception of the unconsolidated cores, were mounted in Hassler holders. Water was used to transmit pressure to the sleeve. The inlet endpiece had two entry ports which permitted scavenging one fluid with another to avoid any mixing in the small holdup volume. The cores were flushed with CO2 gas, evacuated for 5 to 6 hours and saturated with the first liquid at a pressure of 1,000 psi for 24 hours to eliminate any free gas from the cores. Pressure differences up to 20 psi were measured by transducers, calibrated in inches of water and continuously recorded. For greater pressure drops, gauges were used. All reservoir cores were cleaned with a light refined mineral oil, then with heptane, and finally dried with CO2. Compatibility tests showed that no precipitates formed when mineral oil and the crudes were mixed. Some cores were extracted in Dean-Stark-type solvent extractors using xylene and trichloroethane and dried in a vacuum oven at 450F. Each test consisted of a sequence of water, test solution, and again water flow. RESULTS AND DISCUSSION STUDIES IN BEREA CORES Salinity Contrast Berea cores 2-in. in diameter and 12-in. long were cut from sandstone quarried in Cleveland, Ohio. The clay minerals were identified by X-ray diffraction to be chlorite, kaolinite, illite and incerlayered illite. Flow of fresh water or 30,000 ppm brinc does not cause any permeability reduction (Fig. 1). However, after injection of brine the core is readily damaged by fresh water. Damage starts almost instantly as the fresh water injection is begun, and at a cumulative injection of 1.2 PV fresh water, the permeability has dropped from 190 to 0.9 md. Upon continued injection, the effluent contains clay minerals dislodged from the core. The final core per-

Jan 1, 1966

By A. S. Grove, C. T. Sah, E. H. Snow, B. E. Deal

A summary of- several recent investigations in to the properties of the metal-oxide-silicon system is presented. A major portion of these studies makes use of the MOS capacitance-z)oltage method of' analysis. The particular areas of investigation which are reported include: 1) a general survey of the electvical properties of thermally oxidized silicon surjbccs; 2) a study of ion migration through silicon dioxide films ; 3) measurements of electron and hole mobilities in surface inversion layers; 4) a study of impurity redistribution due to thermal o.ridatiotz; and 5) measurements of the rates of oxidation oj-heavily doper7. silicon. THE importance of the metal-oxide-semiconductor (MOS) system in the semiconductor industry is well-known. In addition to its importance in the "planar" device technology,' the MOS structure is now also used in the fabrication of active solid-state devices. Consequently, extensive efforts have been made recently to obtain a better understanding of the characteristics of this system. A summary of some studies of the MOS system conducted in our laboratories during the past year is presented. For the most part these studies used silicon as the semiconductor, along with silicon dioxide and aluminum as the other two components of the system. Since the MOS capacitance-voltage method of analysis was used extensively in these studies, we will first briefly describe its nature and consider some of the possible causes of deviation of experimental observations from the simple theory. We will then outline the various related areas of investigation carried out in our laboratories and will briefly indicate some of the results. It should be noted that the purpose of this paper is merely to provide a brief summary of MOS studies. More detailed discussions of the various areas of investigation are given in the references cited. PRINCIPLES OF THE MOS C-V METHOD OF ANALYSIS' A sketch of the MOS structure is shown in the upper portion of Fig. 1. In this case the insulating film is Si02 and the semiconductor p-type silicon. If a large negative bias is applied to the metal field plate, holes are attracted to the silicon surface. The silicon then behaves much like a metal and the capacitance measured is that of the oxide layer alone, Co. If a small positive bias is applied to the aluminum, holes are repelled and a region depleted of majority carriers is formed at the silicon surface. This depletion I-egion adds to the width of the dielectric and the measured capacitance begins to drop. With increasing positive bias, the width of the electrical depletion region increases. At some large positive bias an inzevsion regiotr is formed at the surface and additional charges induced in the silicon appear in the form of electrons in this narrow inversion region. Thus the depletion-region width approaches a maximum value and, consequently, the capacitance reaches a minimum value and then either levels off or rises again depending on the measurement frequency and the rate of equilibration of the minority carriers in the inversion layer.3 Band diagrams, along with the corresponding charge distributions, are shown in Fig. 1 for the above bias conditions. If minority carriers cannot accumulate at the surface to form an inversion region, the depletion-region width continues to increase with increased positive bias and the capacitance drops toward zero as in a reverse biased p-n junction. The effect of a work-function difference $hs between the metal and the silicon, and of surface charges per unit area Qss located at the oxide-silicon interface, is simply to attract charges in the silicon much like the applied bias. It can be shown that this results in a parallel shift of the capacitance-voltage characteristic along the voltage axis by an amount corresponding to AV = -$bIs + Qss/Co. Theoretical curves have been calculated4 giving the capacitance of the MOS structure C normalized to the oxide capacitance Co vs the quantity VG here VG is the voltage applied to the metal field plate. In Fig. 2 such calculations are shown as points for a particular oxide thickness and bulk impurity concentration for a p-type semiconductor. (For an n-type semiconductor the curves would be mirror images of these.) All three cases, i.e., low frequency. high frequency, and depletion, are indicated. Also shown in the figure are recorder tracings of the characteristics of actual devices. These characteristics have been shifted along the voltage axis to compensate the effect of surface charges and work-function difference. It is evident that agreement between experiment and theory is good. The nature of this shift along the voltage axis is

Jan 1, 1965

By John E. Riddell

This review is based on a questionnaire sent out in 1959 to 24 Canadian exploration companies, known to be active in the mineral exploration field, concerning their practice in the use of applied geo-chemical techniques in Precambrian terrains. Of the companies questioned, 21 returned completed questionnaires and of these, 15 companies stated that they had some experience in this type of work. Of the companies who stated that they had no experience in geochemical prospecting in glaciated Precambrian areas it is interesting to note that only three have reported that they do not use applied geochemistry at all. The others have reported that they make use of applied geochemistry in New Brunswick and in the Cordillera in areas of light glaciation. Their opinion is that it is a useful aid when accompanied by other techniques in evaluating mineralized areas. GEOCHEMICAL SURVEYS Table I reviews the type of geochemical surveys used by these companies, and the following points of interest should be noted.

Jan 11, 1960