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By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By HENRY JULLUM

THE ARGONAUT' mill stands at the crest and spreads down the western slope' of a hill, which incidentally covers the' outcrop of the Argonaut vein' at this point. The collar of the main shaft of the mine is situated on the eastern slope of the same hill 120 ft. below the highest ?point. The present mill, built in 1916, was designed to treat 250 tons per 24-hr. day. This capacity has not been attained recently owing to the inability of the mine to produce enough ore while extensive development and underground construction were under way. At present, however, the mine is more than able to take care of the mill requirements.

Jan 1, 1932

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and visitors who registered at Institute headquarters during November: George W. Otterson, Mauson, B. C. Roy H. Allen, Chihuahua, Mexico. E. L. C. Ayres, Bound, Brook, N. J. George A. Packard, Boston, Mass. M. Russell, Bound Brook, N. J. Richard C. Patterson, Jr., Kansas City,,Mo. Carlo Spruyt, Antwerp, Belgium. Francis C. Phillip, Pittsburg, Pa. Charles A. Pringle, San Francisco, Cal. M. H. Kuryla, Mexico City, Mexico. E. S. Bardwell, Great Falls, Mont. Arthur Chippendale, Mexico City, Mexico. Sir Robert Hadfield, London,, England. F. Danvers Power, Sydney, Australia. James A. Barr, San Francisco, Cal..

Jan 12, 1913

By J. J. Gilman

WHEN a zinc crystal is immersed in liquid N, and then plastically bent, it is observed that it bends a certain amount and then fractures. This fracture occurs at a fairly reproducible radius of curvature, and the radius varies systematically with the crystal orientation. Because this phenomenon provides an unusually well-defined set of fracture conditions, it is possible to examine various possible fracture criteria and select the best one. Zinc crystals of various orientations were bent about axes lying in their glide planes (0001) and perpendicular to their glide directions [1210]. The crystals were 0.150 in. diam and had chemically polished surfaces. They were immersed in liquid N, while they were being loaded on an Instron testing machine. A three-point bending jig was used to load them. Table I lists the beam radius at which fracture occurred for each orientation. Each value is the average of at least six measurements. The normal stresses on the cleavage planes, at the time of fracture, were calculated as follows: First, from the fracture radius, R,, the orientation angle, x,, of the (0001) plane at the outer fiber was calculated. If x, = angle between the (0001) and the rod axis prior to bending, d = rod diameter, and X, = angle between the (0001) plane and a tangent to the bent crystal, then1 sinX, _ 2R, sin xn 2R, + d Since the glide shear strain is given by' y ' cot X, — Xo the glide strain at fracture, x,, can be calculated. Next, it is necessary to know the tangential stress in the outer fiber at fracture. This depends on the plastic flow curve, so a series of tensile tests were performed at —196°C on another set of zinc crystals. A curve of the average resolved shear stress versus glide strain was prepared. From this curve, shear stresses, r,, corresponding to the glide strains in the bend tests were taken. These values are listed in Table I. Then the normal stresses in the outer fibres, u,, were calculated from the relation U, = r, tan X, This analysis assumes that the fiber stresses in a bent beam are the same as the stresses in simple

Jan 1, 1959

By F. W. SUTTER

IN order to have ore available on the completion of the beneficiation plant at Clifton and to provide for continuous production while underground development was carried out, it was decided to develop an open-pit through the crest of a long hill in which the ore outcropped, using 40-ft. vertical benches.

Jan 1, 1943

By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600' to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k'?, where k' is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook' and by McAdams and Geil.' The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton' indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

By Orvar Nyquist, Klaus W. K. Lange, John Chipman

Liquid Fe-C-Si alloys containing 0 to 12 pet Si and up to 4 pet C were equilibrated with carburizing gases at 1550°C. Two to 5 alloys simultaneously were held in close proximity for 5 to 7 hr to establish uniform carbon activity in the group. Analysis of the data gives the activity coefficient of carbon as a function of the mole fractions of carbon and silicon, Fig. 7. Values of the interaction coefficients at infinite dilution are

Jan 1, 1962

AT the Tulsa meeting of the A. P. I., the following reso-lutions, expressive of the policy of that organization, were among those adopted: RESOLVED, That we endorse the conclusion of the Federal Oil Conservation Board in its report of September, 1926, that the prevention of the waste of gas incident to the pro-duction of oil is of paramount importance in the conserva-tion and economical production of oil, and the president of the Institute is requested to appoint a committee of seven to devise and suggest to this board, or the executive com-mittee, such measures as will enable the industry, while continuing to meet the consumption requirements for pe-troleum and its products, to conserve in its natural state such reserves of petroleum as may not then be required for consumption. RESOLVED, That the president of the Institute appoint a committee of seven to formulate and recommend to this board or its executive committee, at the earliest practicable date, a program of legislation; Federal and State, to be advocated by the Institute giving sanction and effect to agreements by oil producers for the curtailment of produc-tion in pools where and during periods when there is over-production, having for their purpose the economical and orderly production of oil.

Jan 1, 1927

By A. W. Gauger

Fox perhaps one hundred years scientists have been engaged in attempts at devising a satisfactory method of classification of coal. During this time many charts, tables and graphs have been proposed, some of which have had considerable merit, but no one system has been found to be applicable to all ranks of coal, nor has any one system received general acceptance. In many of the proposals, water eliminated between room temperature and 105° C. has been regarded as extraneous matter and calculations have been made to the air-dry or water-free basis. Such methods of. calculation do not lend themselves to satisfactory grouping of the high-moisture coals.1,2 A consideration not only of the properties of the high-moisture coals and their behavior on drying but of the generally accepted ideas of the coalification process and the role of water in this process indicates that water is an essential constituent of all coals and therefore should not be neglected. For example, in such low-rank coals as the lignites of the Northern Great Plains' deposits the inherent moisture of the lignite as mined plays a very important part in the physical properties thereof. Freshly mined lignite contains upwards of 30 per cent water and is extremely tough and resistant to shock. Upon exposure to the atmosphere, the lump loses part of its moisture and checks and splits, leaving a friable and broken up residue. So far as we have been able to determine, water is the only thing lost in this process and we are forced to the conclusion that moisture plays an extremely important part in the structural properties of the original lignite. With reference to the coalification process, Mack and Hulett3 pointed out in 1917 the important part that water played therein. They observed that water cannot be removed from peat or coal by pressure alone, but only as the result of chemical reaction, and suggested that peat in its early stages may be largely a hydrosol. Slow chemical changes occur over a long period of time until finally the mass becomes more largely a hydrogel. These views are substantiated to some extent by the experi-

Jan 1, 1932

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 E. T. Turkdogan, P. Grieveson

STAFF: Editor, Gerhard Derge Acting Editor, Paul G. Shewmon Carnegie lnstitute of Technology Sc hen ley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Karl L. Fetters, President; J.S. Smart, Jr., Past-President; R. C. Cole, Vice President; R. L. Hennebach, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: W. 0. Phil-brook, Chairman; H. L. Bishop, R. C. Cole, J. N. Hobstetter, W. A. Krivsky, E. R. Morgan, F. C. Langenberg, R. E. Lund, Paul Queneau, L. L. Seigle, R. L. Smith, and T. '4. Wainwright. Review and selection of manuscripts is under the supervision of the following Publications Committes: Extractive Metallurgy Division: R. E. Lund, Chatrmon; M. E. Wodsworth, Vice Chairman; D. H. Baker, Jr., G. M. Bell, R. E. Groce, W. A. Krivsky, R. A. Lewls, Charles O'Neill, A. W. Schlechten, R. E. Shinkoskey, and W. W. Stephens. Iron and Steel Division: T. V. Wainright, Choirman; H. L. Bishop, R. E. Boni, T. E. Dancy, C. W. Murphy, Johonnes M. Uys, J. B. Wagstaff, and R. G. Ward. lnstitute of Metols Division: J. N. Hobstetter, Chairman; P. A. Beck, J. J. Becker, G. F. Bolling, J. O. Brittain, J. 8. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, L. R. Girifalco, J. C. Gurland, H. S. Kclish, E. L. Harmon, J. J. Heger, A. A. Hendrickson, L. Himmel, J. P. Hirth, H. H. Johnson, Jr., R. R. Nosh, T. N. Rhodin, R. H. Richman, H. C. Rogers, W. Rostoker, C. Sherby, C. W. Spencer, L. Slifkin, J. K. Stanley, R. Steinitz, H. C. Stumpf, and R. Swolin. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 345 East 47th Street, New York 17. N. Y. Telephone PLaza 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign; $7.50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement made or opinion expressed in its publications ... Copyright 1962 by the American lnstitute of Mining, Metollurgical. and Petroleum Engineers. Inc. . . . Registered cable address, AlME New York . . . Indexed in Engineering Index, lndustriol Arts Index, and Chemical Abstracts . . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 224, Number 6.

Jan 1, 1962

By Guy Borden, Michael J. Rzasa

Laboratory data on bubble point pressures and reservoir volume factors have been correlated as functions of solution gas-oil ratio, calculated gas gravity of the pentanes-and-lighter fraction of the entire fluid, differential residual oil gravity, and reservoir temperatures. INTRODUCTION Several correlations of crude oil properties have appeared in the literature. D. L. Katz4 in 1942 presented five methods of predicting oil shrinkage. these being of decreasing accuracy for decreasing amounts of information available. M. B. Standing- in 1947 published three correlations of laboratory flash vaporization data of California crudes. From values of GOR (gas-oil ratio), gas gravity, liquid gravity, and temperature, his correlations will predict bubble point pressure, formation volumes of bubble point liquids, and two-phase formation volumes. Curtis and Brinkley2 in 1949 presented several correlations. From the gas-oil ratio, an approximation of reservoir volume factor and barrels of condensate recoverable per barrel of reservoir space may be obtained; along with liquid gravity and reservoir temperature, the GOR will allow prediction of bubble point pressure. These last cor- relations seem to be more qualitative than quantitative. Generally, laboratory bottom hole sample tests furnish information on solution gas-oil ratios, residual oil gravities. bubble point pressures, viscosities of oils, liquid shrinkages, and occasionally gas gravities. Each of these data has its own applications and use in reservoir engineering calculations. The particular uses of correlated bottom hole sample data are found in (1 Providing a basis for obtaining estimates of formation crude properties in fields where bottom hole sampling is impractical or impossible. (2) Greatly reducing the time in obtaining the desired information. (3) Determining the applicability of the results from various bottom hole samples to particular field problems. (4) Avoiding, in many cases, the uncertainties of sampling by replacing it with an element over which greater control can be exercised. (5) Permitting use of preliminary field data in application of production procedures before a bottom hole sample can be obtained and analyzed in the laboratory. (6) Serving as a check on data which may appear out of line. (7) Estimating for a particular type crude the appropriate equilibrium constants by working backward from the bubble point pressure. (8) Estimating original or other past history properties of reservoirs that were not sampled in the past. PROCEDURE Application of the published correlations4,6 to Stanolind laboratory data indicated that the general scheme presented by Standing" could give dedrable results if changes were made in parameter positions and scales. The correlation curves were drawn with all the variables having consistent gradations except the temperature increments which were drawn in to best fit the data. The variables from available Stanolind laboratory data are defined below: (1) Gas-oil Ratio: Gas is liberated at reservoir temperature by differential vaporization (or rather by a series of flashes, approaching differential vaporization) and measured at atmospheric pressure and temperature, at which the compressibility factor is assumed to be unity. The oil is the residual liquid remaining after the pressure has been reduced to atmospheric. For the gas-oil ratio both volumes are corrected to standard conditions of 14.7 psia and 60°F. (2) Gas Gravity: It was decided to arbitrarily divide the hydrocarbons of the entire bottom hole sample into pentanes-and-lighter and hex-anes-and-heavier, and use a calculated gas gravity of the pentanes-and-lighter for a correlating variable. (Sample calculation is shown in Table 111.) (3) Liquid Gravity: This is the API gravity of the residual liquid from the differential vaporization. The gravity is measured at room temperature and corrected to 60°F.

Jan 1, 1950

By A. W. Gauger

For perhaps one hundred years scientists have been engaged in attempts at devising a satisfactory method of classification of coal. During this time many charts, tables and graphs have been proposed, some of which have had considerable merit, but no one system has been found to be applicable to all ranks of coal, nor has any one system received general acceptance. In many of the proposals, water eliminated between room temperature and 105" C. has been regarded as extraneous matter and calculations have been made to the air-dry or water-free basis. Such methods of calculation do not lend themselves to satisfactory grouping of the high-moisture coals.1, 2 A consideration not only of the properties of the high-moisture coals and their behavior on drying but of the generally accepted ideas of the coalification process and the role of water in this process indicates that water is an essential constituent of all coals and therefore should not be neglected. For example, in such low-rank coals as the lignites of the Northern Great Plains' deposits the inherent moisture of the lignite as mined plays a very important part in the physical properties thereof. Freshly mined lignite contains upwards of 30 per cent water and is extremely tough and resistant to shock. Upon exposure to the atmosphere, the lump loses part of its moisture and checks and splits, leaving a friable and broken up residue. So far as we have been able to determine, water is the only thing lost in this process and we are forced to the conclusion that moisture plays an extremely important part in the structural properties of the original lignite. With reference to the coalification process, Mack and Hulett3 pointed out in 1917 the important part that water played therein. They observed that water cannot be removed from peat or coal by pressure alone, but only as the result of chemical reaction, and suggested that peat in its early stages may be largely a hydrosol. Slow chemical changes occur over a long period of time until finally the mass becomes more largely a hydrogel. These views are substantiated to some extent by the experi-

Jan 1, 1932

By A. L. Mular

lnput energy-size modulus relation at small reduc-tion ratios is expressed by Et = (M, -Mt) k;. In some cases 13 is close to Schuhmann's distribution modulus a in value. Experimental results in conjunc-tion with the equation demonstrate the fact that energy input which produced fracture is not expended on unbroken starting material inside the mill at any time. Recently, schuhmann1 derived the Charles equation2 using the postulate that complex com-minution operations can be considered as a summa- tion of many comminution events. The fragments resulting from each event are assumed to follow the Gaudin-Schuhmamn distribution. In his derivation, Schuhmann implies that the size distribution of the total mass of a material is determined by the fraction of that mass actually subjected to comminution. Consider a feed to contain a volume, Vo, of uni- formly sized homogeneous material. After t seconds of grinding, let the volume of broken material be Vo - Vt where Vt is the volume of starting material not yet broken. The size distribution of the broken material is given by: where V is the cumulative volume less than size X, and k, is the size modulus of the broken material at time t. The distribution for the total volume at this

Jan 1, 1962

By Frederick V. Lawrence

Broadly speaking, fluxes are substances which promote wetting and spreading or enhance the fluidity and manipulative properties of materials in joining, fusion, and smelting operations. The term most strictly applies to substances used to facilitate soldering and brazing; but in the discussion which follows, the definition will be broadened to include materials used to promote fusion in arc welding and which aid in the smelting of metals. In each of the mentioned applications, the role of flux and its composition differs considerably; consequently in the discussion which follows, fluxes for soldering, brazing, arc welding, and smelting applications will be considered separately. Soldering and Brazing Fluxes Soldering and brazing are metallurgical joining processes in which a joint is formed using a filler metal of composition dissimilar to that of the joined pieces (base metal). The filler metal, solder or braze, is always of lower melting point than the base metal. Consequently with these processes there is no melting of the base metal. The successful creation of the joint depends upon the wetting and spreading of the solder or braze around or throughout the joint. The obstacles to successful soldering and brazing are contaminants and tenacious oxide films on the metal surfaces. In soldering and brazing applications, fluxes act to remove and exclude oxides and other impurities from the joint. There is no fundamental difference between soldering and brazing. The distinction between them is made on the basis of temperature. Join¬ing operations carried out at temperatures above 500° C are termed brazing. The higher temperatures used in brazing enable higher melting point filler metals to be used which generally provide stronger joints. The higher temperatures of brazing processes also require fluxes which are substantially different from those used in soldering and which will remain effective at high temperatures. Consequently the distinction between soldering and brazing can also be made on the basis of the fluxes used. Soldering Fluxes Even thoroughly cleaned and degreased, metal surfaces still possess tenacious oxide films which inhibit the soldering of the joint. The reactions which form these films increase with increasing temperature. The rate of oxide formation and the tenacity of the film varies with each base metal. Aluminum, magnesium, stainless and high alloy steels, aluminum and silicon bronzes when exposed to air form hard, adherent oxide films. These metals require highly active and corrosive fluxes to remove and prevent the reformation of oxide films during soldering. Metals such as copper and silver, on the contrary, form less tenacious films at a lower rate, so that mild fluxes are sufficient. Soldering fluxes must dissolve or remove oxides and promote rapid wetting and spreading of the solder. The flux removes the oxide film by loosening and floating it off into the main body of the flux. The oxide removal is often aided by the alloying of the solder with the base metal, undermining small areas of the oxide and detaching them (Anon., 1959). The flux coagulates and suspends the oxide particles which have been loosened. The flux forms a protective cover preventing the reformation of the oxides, permitting the spreading of the solder and the formation of a metallic bond between the solder and the base metal. Constituents of Soldering Fluxes: Soldering fluxes are commonly grouped into three categories: highly corrosive, intermediate, and noncorrosive. One normally would choose to use the least corrosive flux which will give satisfactory performance.

Jan 1, 1983

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10' cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;' the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson's equation is

Jan 1, 1965

By WALDEMAR T. SCHALLER, EDWARD P. HENDERSON

THE material available for mineralogic study, consisted of drill cores, 2 to 3 in. thick, supplemented by small well cuttings. Such study has added no essential new information regarding the minerals, though the refractive indices, used for determinative purposes, have been determined more accurately than before, permitting the development of a scheme for the rapid identification of these minerals. The essential points brought out by the investigation are two: (1) that certain mineral associations evidently point the way to an understanding of the geologic history and (2) that a definite sequence of mineral formation has taken place so that the original minerals formed have been in part-reacted on producing new compounds and associations; Twenty minerals have been found. The most important are :

Jan 1, 1929

By Elmars Ence, Harold Margolin

The partial isothermal section of the Ti-Cu-Zr system at 750°C has been studied. The crystal structure of Ti2Cu has been detevnlined as tetragonal and when expressed as face-centered tetragonal, a = 4.164, c = 3.611 A, and c/a = 0.867. TITANIUM systems in which ß-titanium decomposes eutectoidally into a and a compound rather readily are known as active eutectoid systems. Recently in active eutectoid alloys based on the Ti-Cu system, and containing additionally A1 and Zr, it has been found that zirconium may produce both moderate weakening and marked strengthening at elevated temperatures.' In order to obtain some insight into the behavior of zirconium, an attempt was made to determine whether compounds of the type Tix Zr and TixZryCu exist. Only results of the Ti-Zr-Cu studies are reported here since data on Ti-Zr alloys will be presented in a separate publication. EXPERIMENTAL PROCEDURE Alloys were nonconsumably arc melted in argon atmosphere as 15-g buttons, prepared from materials of the following purities: Bureau of Mines electrolytic Ti — Bhn 63 OFHC copper Reactor Grade Zirconium Bhn .C 150 Prior to alloy preparation the electrolytic titanium was premelted to avoid excessive spattering of the charges during melting. The weight losses during melting did not exceed 1 pct of the total weight of the charge. The alloys prepared are listed in Table I together with analyzed compositions. in cases where they were determined. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. About 1 to 2 sec are required to remove the capsule from the furnace, drop it into the iced brine and break it. Because of the insulation effect of the quartz, this delay in quenching should not produce a large drop in temperature. In many instances, no difference or little difference has been detected between the same specimen quartz capsule quenched or directly quenched in vacuum by an impinging stream of water.' Ti-Cu-Zr alloys were homogenized for 48 hr at 825°C prior to annealing at 750°C. Annealing for 5 days at 750°C produced the same results as 11 days at temperature and it was therefore assumed that 5 days was sufficient to establish equilibrium. Titanium-copper alloys were homogenized for 40 hr at 900°C prior to heat treatment for 6 days at 750°C. Specimens for metallographic examination were electropolished and etched with the following solution:

Jan 1, 1962

By Joseph J. Becker

RECENTLY the "oriented growth" hypothesis of recrystallization textures has been receiving considerable attention. According to this view, "whenever a new generation of grains is growing in a highly oriented matrix . . . one may assume . . . that from among available nuclei of a great variety of orientations those with suitable orientation relationship with respect to the matrix have by far the highest rate of growth (oriented growth) and will, therefore, predominate."' This statement includes primary recrystallization of single crystals and of polycrystalline materials showing strong deformation textures as particular cases. While the phenomenon of oriented growth undoubtedly does operate, and may be of importance in coarsening or secondary recrystallization, the writer feels that its extension to primary recrystallization is a different matter. Several aspects of this phenomenon may be pointed out which are difficult to rationalize on the basis of oriented growth. In recrystallizing deformed single crystals of alpha brass, Maddin, Mathewson, and Hibbard2 found that the twin composition planes of the recrystallized grains were parallel to the three operative slip planes they observed, and not to the fourth octahedral plane. The writer's current work seems to indicate further that when only one or two slip systems can be seen to operate, the recrystallized grains are aligned only with those slip planes actually observed. This behavior could hardly be accounted for by oriented growth, because on the latter basis the recrystallized texture of a deformed single crystal should certainly have the same symmetry as the crystal itself. Growth rates could not be expected to distinguish between crystallogra- phically equivalent directions, unless the presence of a visible slip system vastly increases the growth rate in the appropriate direction. This seems unlikely. These relationships were observed by the writer only when considerable care had been exercised before annealing to etch away the effects of cutting out the centers of tensile specimens with a jeweler's saw and to etch off the ends of compression specimens. When these.precautions were not taken, nu-cleation inevitably appeared to occur at the saw cuts or at the ends, and the resulting orientations never showed a [111] rotation but appeared quite random. The provision of many nuclei of many orientations did not enhance the correlation, but destroyed it. Recrystallization textures are sometimes strongly dependent on annealing temperature, which would imply that the anisotropy of growth rates is a suddenly varying function of temperature. This might be regarded as unlikely. Recrystallization textures can be strongly dependent on the degree of deformation. If textures are to be explained by selective growth from among nuclei of all orientations, it is difficult to see how the recrystallization process could have any dependence whatever on the manner or degree of deformation. It is felt that the above points should be considered before the oriented growth hypothesis is applied to primary recrystallization, with the necessary complete divorce of the mechanism of recrystallization from the details of the deformation process. References 1P. A. Beck and H. Hu: Reply to discussion of their paper on Recrystallization Texture and Coarsening Texture in High Purity Aluminum. Trans. AIME, 188, 1057; Journal oF Metals (Aug. 1950) TP 29083. 'R. Maddin, C. H. Mathewson, and W. R. Hibbard, Jr.: The Origin of Annealing Twins in Brass. Trans. AIME, 185, 655; Journal of Metals (Sept. 1949) TP 26763.

Jan 1, 1952

By R. T. DeHoff, L. J. Buteau, J. Kronsbein

Network topology is introduced and used to describe sinter bodies at various stages of the sintering process. The matrices of incidence, loop-branch. tree-branch, and cut-branch are constructed and their relationship to the three-dimensional void space and the common two-dimensional bounding surface is established. The sintering body is assunzed to remain connected but this is not so with the void space. The topological invariants known as Betti numbers are related to this observed fact and provide parameters which measure the progress of the sintering process. They are extracted from the matrices by means of known algebraic operations. Experimental procedures are given which permit actual construction of the various matrices and determination of the Betti numbers by serial sectioning of the sinter bodies. A sinter body is produced by exposing a large number of metallic particles (0.00001 to 0.3 in. diam) to a temperature that is near but below their melting point. When these particles are maintained at such a temperature for a sufficient length of time, it is found that the interparticle contacts become welded. As time increases, these welds, often referred to as necks, grow. All of the space between the particles constitutes a single connected void; an ultimate consequence of sintering is the breaking up of the void into separated parts. A mathematical apparatus for describing the geometric characteristics of a sinter body at each stage of the process was first proposed by F. N. Rhinesl when he introduced the application of topology to this problem. He described the sinter body in terms of one of its topological invariants, the genus. The most important advantage of a topological description is invariance with respect to continuous deformations. This means that particle sizes and shapes need not be considered, resulting in considerable simplification and generalization of the geometric description. In the case of a sinter body, wherein the internal geometry is particularly complex, the simplification provided by topological concepts is absolutely essential. The important parameters in the Rhines model are the number of particles and the interparticle contacts. The invariant considered called genus is given by Euler's formula for the connectivity of two-dimensional surface of the sinter body. This surface includes the pore-solid interface. The Euler formula is G = C - P + 1 [1] where C = number of interparticle contacts, P = number of particles, and G = genus of the surface bounding the sinter body. In topology the term genus may be used to mean the number of self re-entrant cuts that can be made on a closed surface without dissecting it into more than one connected surface. Its use is restricted to the surface and does not apply to the three-dimensional volume enclosed or excluded by it. In the case of sintering, the volume enclosed by the surface is defined as the sinter body; the volume excluded will be referred to as the void space. There is an intrinsic reason for using genus as a characteristic number associated with a sinter body. The genus is related to the Gaussian curvature by the integral of the product of the principal curvatures taken over the entire surface of the sinter body, as given by

Jan 1, 1965