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By C. S. Barrett, J. E. Burke

The fine lines shown in Fig I are typical of markings that ma): be detected after polishing and etching deformed specimens of alpha brass and other alloys. Although they have long been the subject of discussion by metallurgists their nature is still uncertain and the names that have been applied: to them, such as deformation line4 or strain markinas, indicate this uncertainky. In this paper which repotts the results of a furthcr investigatinn of their nature, they will be called strain mxrkings. Introduction Mathewson and Phillips1 described strain markinps in 1 916 and concluded that they appear only after 20 pet deformation. They objected to the markings being called slip tines believing this term should be sewrved for surface markings protluced by plastic deformntion. In 1921. vogel² described similar striations which appeared after polishing and etching the roughly ground surface of numerous alloys. He reported that the markings were crystallo-graphic in nature, and since they resemble Seumann hands in iron, at least superficially, he assumed them to be mechanical twins. In 1928, Matherwson reported work by Phillips which indicated that the lines were more readily produced by impact than by slow deformation and that in many cases the twins inside recrystallized grains were parallel to strain markings in the original deformed grains. This was taken as cvirlence that the markings coalesce into anncaling twins. and hence that they themselves are mechanical twins. Many attempts have been made to demonstrate directly that the markings are mechanical twins. In 1934, Samans described the results of X ray studies of two defomed crystals of alpha brass. Evidence was obtained which could be interpreted to indicate that the strain markings arc mechanical twins, and this remains the only direct evidence to this effect. Several other attempts to obtain similar evidence by X ray diffraction have failed5.8.7 although in no Ease was the original method of Samans employed. An

Jan 1, 1949

By Walter R. Hibbard

THE term lineage was first introduced by Buerger1 to denote dendritic branches, grown from a crystal nucleus during solidification from the liquid, with imperfections in alignment of the order of 10-1 [ ] to 10-4 cm. These imperfections are associated with distortions of the dendrites caused by the subsequent solidification of the inter-dendritic filling and are illustrated in Fig 11. Buerger etched zinc single crystals made by the Bridgman2 method to develop this dendritic pattern and show lineage microscopically. Since maximum crystal growth in face-centered cubic metals occurs along the [100] directions,2 lineage would appear in copper as small deviations of dendritic branches from these directions. Elam4 and others5-8 reported etching effects resulting from coring along the cube face traces of various copper alloy crystals. These traces were used by Samans8 to orient single crystals. Williamson9 noted a "lined structure (in alpha brass single crystals) consisting of an ordered arrangement of etch pits" which were probably traces of {100} planes but somewhat uncertain because they were never straight (i.e., apparently lineage). Greninger10 described the distortion and multiplicity of Laue spots in back reflection X ray photograms of copper single crystals showing lineage. The present investigation includes metallographic, X ray and property studies of lineage in large grain and single crystal specimens of copper. PREPARATION OF SPECIMENS Specimens 10 in. long and ½ in. diam of oxygen-free copper (O.F.H.C.) (99.985 pct) were melted vertically in graphite crucibles under an atmosphere of commercial nitrogen purified through a gas train including sulfuric acid, potassium chloride, magnesium chlorate, hot copper chips and phosphorus pentoxide. After a temperature of 1200°C had been maintained for ½ hr, the furnace was turned off and the specimens cooled at a rate of about 150°C an hour. This method of direct solidification was used by Greninger10 to produce single crystals with marked lineage and in this investigation produced a fair yield of single crystal specimens in

Jan 1, 1947

By M. Gensamer

ALTHOUGH a large number of X-ray photograms of cold-rolled steel have been published, two circumstances have led to the experimental work reported in this paper. The first is that no complete study, making use of the pole-figure method of Wever1, has been made of cold-rolled low-carbon steel. Wever has published pole figures of mild steel sub-jected to plane parallel deformation1,2 and undoubtedly he has applied the method to cold-rolled mild steel, but the authors have not found these data published. Kurdjumow and Sachs3 have applied the method to the study of rolling and recrystallization textures in electrolytic iron; their results will be referred to later. The reason for this dearth of papers using the pole-figure method is obvious; a greater number of photograms and more analytical work (although this work is quite simple and straight-forward) are required to construct a pole figure than most investigators have felt worth while, despite the fact that no other method of which the authors are aware will satisfactorily depict the orientations of the crystal-lites in a polycrystalline aggregate. The second circumstance that led to the work reported in this paper was the appearance of a paper by Wayne A. Sisson4 on the same subject. In his valuable study of the factors influencing the development of pre-ferred orientations in cold-rolled mild steel, Sisson made one observation that required confirmation; that is, that at some stage of the rolling proc-ess the type of preferred orientation changed from the type that gives a photogram characterized as a "six-point" X-ray pattern to that known as a "four-point" pattern. A similar observation had been made by Tam-mann and Heinzel5, who studied the orientations developed in the rolling of steel by the specular reflection of light from the etched surface of rolled samples. These workers also found that the type of preferred orientation

Jan 1, 1936

By A. S. Koster, G. D. Rieck

X-ray experiments were carried out to show the occurrence of cylindrical texture in drawn tungsten wire. Only a small amount of (110) (110) cylindrical texture could he found in wires of intermediate thickness, i.e., of about 1.5 mm diameter. DRAWN wires of tungsten and other bcc metals like iron and molybdenum show a well-established (110) fiber texture. Now it might be conceivable that in drawing radial stresses remove the randomness of the crystallites around the [110} axis, thus giving a fiber texture of higher symmetry. In the resulting so-called cylindrical textures a specified plane normal coincides with the radius of the wire. Several authors discuss the occurrence of cylindrical textures in bcc metals. ~ieck' found no cylindrical texture in drawn tungsten wires of 165 n diameter. Leber~ states that in tungsten wires of 3 mm diameter a cylindrical {100)(110) texture is developed, which is gradually converted to a normal fiber texture by subsequent drawing. He also reported a definite cylindrical texture at the surface of iron wires. Peck and Thomas3 observed a nonuniform mode of deformation of the grains in transverse sections of heavily drawn tungsten and iron wires. According to Bhandary and cullity4 a swaged iron wire has neither a perfect (110) fiber texture nor a perfect {100}(110) cylindrical texture. It is clear that the concept of cylindrical texture in bcc metals still lacks a firm experimental basis. Leber's eviden~e,~ which seems to be the strongest, rests upon qualitative interpretation of photographs. The appearance of the 110 and 200 lines on the photograph of 3-mm wire, however, can be very well attributed5 to a normal ( 110) fiber texture superimposed on random background; our Fig. 1, giving a Debye-Scherrer diagram of etched tungsten wire of 180 p, is free of cylindrical texture according to all authors, but is quite similar to Leber's diagram. It was therefore decided to use a different method of X-ray texture determination on tungsten wires of diameters where cylindrical textures may be expected.

Jan 1, 1965

By W. P. Frey

THE briquet plant of the Lehigh Coal and Navigation Co., at Lansford, Pa., has previously been referred to.1 It has passed. the stage of experiment and now rests,, on a foundation practically and financially sound. The purpose of this paper is to explain how success has been attained, and to set standards for the development of hard-coal briquetting which may eliminate future failures. All the conclusions are based on actual results, avoiding speculation and theory. Up to three years ago, the L. C. & N. Co. used coal-tar pitch as a binder in making hard-coal briquets. The plant operated with a monthly output of 300 to 600 tons and was unable to meet its own expenses. Naturally, no one was satisfied, especially as the ideals of a smokeless briquet were still unrealized. Then came the Dutch oil process, introduced in this country by the General Briquetting Co. of New York. This process uses as binder a small percentage of heavy residue of petroleum, which, being liquid, permits great economy of handling; it also did away with the most objectionable fumes of the former briquets. This oil2 is not absolutely smokeless; heating the fresh fuel to red heat liberates some low-volatile hydrocarbons, yielding a white smoke which is not objectionable. On the other hand, this oil adds to the briquet about 7 per cent. of volatile matter, giving the product a heating capacity equal to that of the best free-burning anthracite coal. The average silt used in the manufacture of these boulets averages 16.5 per cent. chemical ash, corresponding to 12,000 B.t.u. per pound of coal. The Hydrolene used as binder runs about 17,500 B.t.u. per pound, and approximately 7 per cent. of it enters into the mixture, hence 12,000 X 0.93 11,160 B.t.u. 17,500 X 0.07 1,125 B.t.u. Total 12,355 B.t.u. per pound of briquets

Jan 1, 1918

By Robert L. Gower, John H. Cash

Interconnections for integrated circuits operating at rnicrowaue frequencies rzust be formed as microwave transmission lines. This paper describes the fabrication of one type of microwave transmission line known as microstrip, which can be fabricated on momlithic integvated circuits by deposition of 0.1- to 2.0-mil-thick metal and dielectric films. A microstrip line consists of a narrow conducting strip separated from a gvound plane by a dielectric material. Thick films of good conducting materials are required for low loss at high frequencies. Vacuum-evaporation methods for depositing aluminum and silver films are described. The narrow conducting strip forming the top conductor is defined by photoresist-etching techniques after the thick rnetal film is deposited. Gold plating with a photoresist-masking technique is also used to forrrz thick metal conductors. The microstrip dielectric layer is formed by deposition of suitable dielectric films 0.1 to 2.0 mils thick. Several deposition techniques were investigated. Electron-beam evaporation of quartz is described. Electrical characteristics of deposited microstrip lines at microwave frequencies are included and the microwave power attenuation as a function of conductor and dielectric thickness is given. It is concluded that the deposition of microstrip transmission lines is a practical way to achieve low-loss interconnections in monolithic integrated circuits. CONNECTIONS between devices in low-frequency and digital circuits are usually made by connecting the devices with a length of conductor such as a metal lead oi- a wire. If this method were applied to microwave integrated circuits, the reactance of the connection due to the series inductance and parasitic capacitance would be very high, in fact too high to permit successful circuit operation. In addition, resonance and antenna effects would occur at high frequencies, especially when the connections approach the wavelength.' Connections which are sections of transmis- sion line will overcome these difficulties. The electromagnetic field is confined to the volume of the transmission line, parasitic effects are not present, and circuit design utilizes familiar transmission-line techniques. TRANSMISSION LINES One type of transmission line geometrically adaptable to integrated circuits is known as micrstri. A microstrip line can be generated from a coaxial line as shown in Fig. l(a). The outer conductor of the coaxial line is distorted into an ellipse (b) and finally separated at the extremities of the ellipse to form the strip transmission line shown in (c). One of the ground planes is then removed, leaving a conducting ground plane and a narrow conducting strip separated by a dielectric. Two configurations of the microstrip line were considered in this investigation, Fig. 2. Type (a) is fabricated from a semiconductor slice with the ground plane and top conductor deposited on each side of the slice. The semiconductor slice serves as the die lec-

Jan 1, 1967

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.'" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

By Fred P. Peters

At first glance this paper may seem unique among those comprising this symposium on designing for powder metallurgy, since it is evidently concerned with everything but Powder metallurgy. This paradox mill be at once resolved, however, when the real Purpose of the symposium meeting is understood—to present factually and objectively the things that can and cannot he done with powder-metallurgy methods, and especially to set forth with brutal frankness the limitations of Powder metallurgy, so that costly over-enthusiasm and misapplication may be prevented. Since much of powder metallurgy's future development (and many of its present disappointments) has been in competition with other and long-established methods of fabricating parts, it is easy to see that its true competitive possibilities in any given case cannot be accurately appraised without rudimentary knowledge of what the competition can do. This paper, therefore, presents a few reminders of things you all know—a background to be kept in mind as you examine the data on each of their specialties given by the authors of the papers that follow. From the standpoint of the design engineer powder metallurgy is often in Competition with one or more of the following: sand casting, die casting, permanent-mold casting, precision investment casting, ma- chined bar stock, screw-machine parts, cold-heading, drop-forging, and stamping and drawing. We will here briefly discuss each of these individually, and set forth so, rough (and therefore dangerous) generalizations about its competitive position, especially with respect to powder metallurgy. Sand Casting Sand-casting of small parts is sometimes an inexpensive method of manufacture, for its raw-material costs (i,e., for gray iron) are the lowest of the various methods and it involves the use of no tools and dies of jewelry quality. its design flexibility— that is, the ability to make complicated, cored and undercut parts in one piece—is about the highest of the competing processes and in this respect it can do many things that are impossible by powder metallurgy. For small castings its production rates may be higher, by using multi-impression molds, than can be achieved with parts of the same size by powder metallurgy. But its labor charges for melting, pouring, patternmaking and molding are comparatively high and the waste it entails in gates and risers is always considerable. Tolerances of sand castings are wide (+1/6 to 1/32 in- per in.) and where precision approaching that of powder metallurgy is required sand castings must be machined to final size, thus increasing their cost. Steel sand castings are more expensive and less precise than iron, and nonferrous the most costly of all.

Jan 1, 1945

By A. Singh, W. M. Fleming, J. J. Santana, A. E. Torma

The present study investigated the extraction of uranium from a low-grade ore by sulfuric acid and the removal of radium from the leach residues by brine solutions. The optimum leaching conditions were found to be 1.5 mole [£]-1 H2SO4, 6.Og[9]-1NaClO3, 75°C,50% pulp density and 750 rpm with respect to the rate of uranium extraction. The maximum theoretical attainable rate of uranium extraction was determined to be V = 1.09 x 10 -2 mole [¢]-1h-1 with respect to pulp density. The order of reaction was found to be zero regarding the effect of sodium chlorate concentrations. The apparent activation energy of uranium extraction was calculated from the Arrhenius plot to be [A]E a - 2.36 kcal mole-1 (9.87 kJ mole-1). Based on a statistical design, an empirical equation has been developed describing the rate of uranium extraction with the leaching parameters. This equation can be used to generate data which may be useful for scaling up the process to pilot plant level. The most efficient brine solution for the extraction of radium - 226 from the leach residue was found to contain one mole[f] -1 CaCl2 and 0.01 mole [2] -1 HC1. The two step leaching with this solution resulted 87% removal of radium from the leach residue. On the basis of this study, a flow-sheet has been proposed for the extraction of uranium and radionuclides from the ore and leach residue to yield almost innocuous tailings.

Jan 1, 1982

By H. C. Jennison

Two distinct types of defects occur at times in copper wire as a result of the use of dies of improper design or undesirable wire-drawing practice. The conditions under which these defects may be produced, as well as precautions to be taken in order to prevent them, have been known to The American Brass Co. for many years. The quality of the copper wire bars and rods has too often and unjustly been held responsible for these particular defects and it is to correct any such belief that this paper is presented. An extremely high quality of electrolytic copper has been supplied to the trade by all refineries for the last 20 years at least. The purity of the copper would average well above 99.900 per cent. The casting of the wire bars has been handled in a generally satisfactory manner. The bars have been cast sound, with a flat to slightly crowning set and have been free from sloppy edges, cold sets, etc. In other words, the wire bars have met A. S. T. M. specifications and have been generally satisfactory. For the most part, they have been everything that could be desired from a quality standpoint yet most of the wire mills in this country and in Europe have at times held the quality of the copper responsible for the two types of defects described in this paper. As a matter of fact, these defects are produced entirely in the wire mills. The author has visited many of the large wire mills in the United States and in Europe to investigate these defects. In some cases the trouble has been so serious that the wire mill has ceased operations. At times the wire mills are reluctant to believe that they are responsible for the defective product. The effect of die design, wire-drawing practice, etc., upon the quality of copper wire has received little study on the part of wire mills, particularly those that have commenced operations in the last few years. Two Types of Defects One type of defect is generally known in this country as "check marks;" in Europe it is termed "crowfeet" (Fig. 1). This defect occurs in the surface of the copper wire, in the form of V's, which are always

Jan 1, 1930

By AIME AIME

EVEN the weather man joined in a friendly conspiracy to make the fall meeting of the Industrial Minerals Division at Rolla, Mo., Oct. 23-25. the splendid surges that it was. Following weeks of rain, the foliage of the Ozarks was still green, merely enlivened here and there by splashes of autumn coloring. In contrast to the tranquil beauty of the School of Mines campus under smiling Indian summer skies, the pace of the meeting was lively. Registration was larger than at any previous meeting and included an unusual number of prominent names and delegates from all over the country. From 125 to 150 were present throughout the three technical sessions, at the Thursday evening smoker, and also at the banquet on Friday; when students trooped in to the technical sessions the audience was augmented occasionally to over 200.

Jan 1, 1941

By E. L. Anders

The Mile Six pool is located on the La Brea-Parinas Cullcession of International Petroleum Co., Ltd., in northwestern Peru on the west coast of South America. The reservoir pressure in this pool has been maintained within 200 psi of its initial value throughout its history, and gravity drainage has played an important role in the production behavior. It has now produced 95 per cent of its estimated ultimate recovery. It is estimated that this interesting oil pool will ultimately produce 67 per cent of the initial oil in place and that the resulting residual oil saturation may be as low as 19 per cent of the pore volume (29 per cent of the hydrocarbon pore volume). An evaluation of reservoir rock and fluid characteristics and ultimate oil recovery is presented. INTRODUCTION This study of Mile Six pool was made to evaluate its performance according to latest available information. The production performance of this pool has been discussed in various articles in the past. and the reported behavior has been used as an example for application of computation procedures for gravity drainage depletion' and as an illustration of field behavior under gravity drainage or expanding gas cap drive. There have been wide variations in reported values of initial oil in place, reservoir oil volume factor. connate-water sauration, volume of effective sand, and ultimate recovery because of the paucity of reliable basic data. These various factors have been determined as accurately as practicable with the latest available information, and this evaluation is presented herein. The production history of Mile Six is an excellent example of gravity drainage depleion with effective pressure maintenance by gar injection. GENERAL Mile Six pool was discovered by cable-tool drilling in November. 1927. when well 1996 was completed in the Parinas sand. After slow development with cable tools and sporadic production. the pool was opened to continuous pro(iuction in November. 1933. and develpment was completed with rotary rigs. Pressure maintenance was started in December, 1933. by returning gas to upstructure wells. Most of the development was 'completed by 1937, but some additional wells were drilled in the period 1939-1947. and several old wells were deepened. A total of 46 oil and gas wells and 4 dry holes were drilled on approximately 7-acre spacing. Of the producers. 21 are now flowing. 2 are pumping. 44 are gas input wells. 3 are abandoned. I is a gas well shut in. and 15 are shut in because of non-commercial production or high gas-oil ratio. The locations of all wells are shown on the map of Fig. I. Total oil production on Dec. 31. 1952, was 30,867,373 bbl: cumulative gas production was 22,023,777 Mcf; and 26,410,946 Mcf of gas had been returned to the reservoir. These figures do not include oil and gas lost ill a blowout in January. 1940. GEOLOGICAL DESCRIPTION Mile Six pool is located on the northern end of a structural spur projecting from the La Brea-Negritos uplift.' The spur is probably a reflection of a basement structure. It plunges gently to the north, i broken into a complex series of fault blocks. and contain.; the Verdun Alto. Section Sixteen. and Mile Six pools. The Parinas handstone (lower Eocene!. which is the producing formation in Mile Six. occurs at an average depth of 2,200 ft in the pool and dips north and east at from 15' to 20". The pool covers an area of approximately 350 acres. Mile Six is downfaulted about 600 ft from Section Sixteen pool to the soutb. and a major fault forms its western boundarv. The north and east boundaries are formed by the intersection of the sand top with the water-oil contact which occurs at approximately 2.440 ft subsea. An original gas-oil contact probably existed at about 1.875 ft subsea. Fig. 1 presents the latest structural interpretation of the pool. and Fig. 2 is an isopach map showing thickness of the total Parinas formation above the original water-oil contact. The heavy lints of Fig. 1 are contours on the sand top, and the fine lines are contours on the fault planes. This type of straight-line structural map was developed 1)) International's geologists to reflect structural conditions where the bedding planes dip and have no curvature. 'The La Brea-Parinas Concession is highly faulted by normal fault.. The beds are flat wherever exposed. The Parinas formation is approximately 635 ft thick. and it is etimated that 62 percent II the formation is effective sand. The original oil zone was about 565 ft thick. Fig. 211 presents an electric log showing typical Parinas sand development ill Mile Six pool. The Parinas band in Mile Six i. a well-sorted. medium- to-coal-se-grained. cross-bedded sand with minor lenses of shale and small lenses and pockets of pebble conglomerate. The sand grains are subangular to rounded and consist chiefly of quartz with feldspars. biotite hornblende, and augite as accessory minerals. Because of faulting of the Parinas- formation to the east and north of the pool. there is probably l possibility of a significant, natural water drive in Mile six. The faults within the pool. as indicated in Figs. 1 and 2. are of smaller disI,laceInent and seem to act only , partial barriers to fluid movement within the reservoir. RESERVOIR CHARACTERISTICS Core analysis data are available from five wells. The data were obtained from three wells (Nos. 3401. 3586 and 3719) at the time of their completion and from well 1996 when the original liner was sidetracked and the well was deepened ill 1946. Data from well 2779 were obtained in 1943 from old cores taken when the well was deepened in 1934. From these core analyses. the average porosity was estimated to be 22.6 per cent. and the average permeability to dry ail. was estimated to be 780 and Measured productility indices varied from 3.1 to 71.4 B/D per psi differential. Specific productivity indices varied approximately from 0.1 to 0.3 B./D per psi per ft of sand.

Jan 1, 1953

By AIME AIME

A THOROUGHLY satisfactory crowd turned out at the fall meeting of the Industrial Minerals Division and took an active part in the entire program. On Thursday afternoon, Sept. 24, a limestone plant was inspected, technical sessions occupying the attention of the visitors all day Friday and Saturday morning. Headquarters were at the Nittany Lion Inn, an attractive hostel on the Penn State campus, at State College, right in the center of Pennsylvania. We are still in the dark, despite inquiries, as to just what breed of lions Nittany lions are. As nearly as we could find out, Nittany is not a Biblical name, as it sounded to us, but a corruption of the name of an Indian princess, or maiden, or maybe just girl that haunted those parts in bygone times and after whom a near-by mountain was named. Penn State athletes are "lions" and there you are. The meeting was supposed to be a joint one with the American Ceramic Society's Materials and Equipment Division; but it was quite evident that the Institute had a much better publicity agent than the Society, which bothered Ross. Purdy, the aggressive secretary of the ceramic people, no end. However, Secretary Purdy saw to it that everyone present fully understood that the Ceramic Society was present, so that that contingent all but stole the show, its representatives presiding at every meeting. The Pittsburgh Section of the American Ceramic Society was also supposed to be holding its fall meeting there at the same time, but made no trouble at all for anybody, as one of the speakers remarked.

Jan 1, 1936

By M. A. Dayananda, R. E. Grace

Vapor-solid diffusion couples were employed in a study of ternary diffusion in the single-phase copper-rich corner of the Cu-Zn-Mn system Interdiffusion coefficients were measured at three different compositions corresponding to the intersections of diffusion paths determined at 850°C. Intrinsic diffusion coefficients were determined at two compositions by the Philibert-Guy method. New relations between the various intrinsic diffusion coefficients are also presented. MOST of the investigations of ternary diffusion have been made with "sandwich" couples formed by welding together two homogeneous solid solutions with or without markers placed at the interface. With such couples Kirkaldy and his coworkers1,2 have determined interdiffusion coefficients which describe ternary diffusion in the substitutional alloy systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy3 have reported intrinsic diffusion coefficients for Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.4 The use of semi-infinite diffusion couples, for example, vapor-solid couples, where the diffusing species are supplied from a vapor source in contact with a diffusion disk, has so far been confined to studies of binary diffusion. Balluffi et a1.5,6 have successfully determined the interdiffusion as well as the intrinsic diffusion coefficients in several binary metallic systems employing vapor-solid couples with markers initially placed at the vapor-solid interface. They have also discussed the general advantages and limitations of such couples. Vapor-solid diffusion couples can successfully be employed in ternary diffusion studies. The importance of such couples in ternary diffusion lies in the fact that inert markers lie close to the vapor-solid interface, and the composition of the marker plane is virtually known before experimentation begins. Another minor advantage is that the method of Philibert and Guy4 may be used with three alloys instead of four. Lastly, the diffusion paths need not be S-shaped, as pointed out by Meijering7 for "sandwich" couples. The Cu-Zn-Mn system is convenient for ternary diffusion studies because of the large single-phase field in the copper-rich corner. The vapor pressure of zinc above such alloys is known, and X-ray measurements indicate that the molar volume is nearly constant over a wide range of compositions.8,9 It is the purpose of this paper a) to extend the analysis of Balluffi and seigle5 to permit an evaluation of interdiffusion coefficients in ternary vapor-solid couples, b) to use the method of Philibert and Guy to determine intrinsic diffusion coefficients with such couples, and c) to present experimental data on both interdiffusion and intrinsic diffusion coefficients for the Cu-Zn-Mn system at 850°C. INTERDIFFUSION IN TERNARY VAPOR-SOLID COUPLES The analysis of Balluffi and seigle5 is extended in this section to a vapor-solid couple where two solutes diffuse from a vapor source into a ternary solid solution. To take into account the expansion of the diffusion disk caused by the absorption of mass from the vapor phase, the total fluxes are expressed on the basis of a coordinate system that moves with the velocity of the vapor-solid interface; thus. where D3ij are the intrinsic diffusion coefficients,4 v(x, t) is the local Kirkendall velocity of mass flow, and F(t) is the negative velocity of the vapor-solid interface (x = 0). Both these velocities are based on a fixed coordinate system far removed from the diffusion zone. Using the continuity relations and Darken's method1' for a ternary system in which components 1 and 2 diffuse from the vapor phase into a solid of negligible vapor pressure, one obtains

Jan 1, 1965

By C. H. Mathewson

CONSIDERABLE progress has been made during the last few years in analyzing the action of plastic deformation in metallic crystals. This is due largely to the development of X-ray spectrographic methods for studying changes in the orientation of single crystals, or of conglomerates, as they occur during the process of plastic deformation, but partly to the widespread knowledge of suitable technique for preparing large (single or variously combined) crystals for direct crystallographic observation under stress or in various conditions of strain. These two methods of studying changes in the crystalline structure of metals may of course be used in conjunction with features of mutual support, but unfortunately the advantage of direct crystallographic observation is lost when we proceed to the study of severely cold-worked structures, owing to the occurrence of real or apparent crystalline discontinuities which become more and more complicated as the amount of plastic action increases. Furthermore, the X-ray methods do not appear to be adequate, at least in their present stage of development, to fix definitely the character of structural alteration in the parent crystal lattice by plastic deformation. The principal question at issue concerns the nature of the crystalline particles that remain after plastic deformation. These are generally known in our American metallurgical literature as crystalline fragments,1 and they seem, indeed, to diffract as individuals causing the Hull pattern of a, severely cold-worked metal to resemble the pattern of a fine powder,2 with certain features of preferred orientation among the particles determined by the manner and intensity of cold working.

Jan 1, 1927

By Irving Fatt, R. M. Weinbrandt

Efforts have been made for many years to observe pore structure of sedimentary rocks on a microscopic scale. A better description of the pore structure in reservoir rock would aid in the development of relations between flow through tube network models and flow in consolidated reservoir rock. The unique qualities of the scanning electron miscroscope (SEM) make it the ideal tool to use in a study of pore structure. Previous methods of studying pore structure included plastic casts of pore space and optical microscopy.l-7 There is now available a new method to observe three-dimensional flow channels in reservoir rock: a scanning electron microscope having variable magnification from X20 to X20,000 and approximately 1000 times the depth of focus of the conventional light microscopes. This microscope also can obtain stereoscopic images and can measure and diagram flow channels so that it is possible to construct a network of tubes that will model consolidated reservoir rock. THEORY OF THE SCANNING ELECTRON MICROSCOPE The scanning electron microscope (SEM) functions by projecting a beam of electrons through magnetic focusing lenses at a specimen and recording secondary electrons excited by the primary beam. The amount of secondary electron emission portrays the topography of the specimen because more secondary electrons are emitted from high points than from low points. A schematic of the SEM is shown in Fig. 1. The property of the SEM that is of most importance in this study is its great depth of focus. The depth of focus results from using electrons

Jan 1, 1970

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith' indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.'' Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By J. H. Swisher

HIGH-temperature anneals in wet hydrogen are widely used in research as a technique for decarburiz-ing Fe-C alloys. This technique is also used commercially in processing low-carbon steels for magnetic applications. The results of some calculations to be presented show that for temperatures up to 1100°C there is a critical temperature for maximizing the decarburization rate of alloys containing about 0.1 pct C. The low-temperature portion of the iron side of the Fe-C phase diagram1 is reproduced in Fig. 1. Preliminary calculations show that the critical temperature is between 727" and 905°C. In this range, the alloy contains two phases during heat treatment, ferrite and austenite. Decarburization therefore occurs by a process termed "diffusion accompanied by a phase change".' For intermediate stages of decarburization, the carbon concentration profile in a flat plate is shown in Fig. 2. The carbon content increases linearly from zero at the surface to a value, cB , at the two-phase boundary. cB is known from the phase diagram, see Fig. 1. At the interface where x = 5, the carbon content increases to ci, the initial concentration in the alloy. smith3 has derived an equation which describes the rate of movement of the boundary. With a rearrange-

Jan 1, 1969

By K. G. Davis, P. Fryzuk

The diffusivity of silver in liquid tin has been determined, using the capillavy-reservoir technique, over the temperature range 250° to 500°C. The new value, D = 2.5 x 10'* exp(-2480/ RT) sq cm per sec, differs from that obtained by other workers in an earlier investigation. The analysis of data from the capillary-reservoir technique is discussed. In a recent investigation of the solidification of dilute alloys, values for the diffusion constant of silver in liquid tin were required in the analysis of the formation of impurity substructures. AS a result, measurements were made of the diffusion constants in the temperature range 250° to 500°C (melting point of tin 232°C), for the alloy concentrations used in the solidification experiments and at higher concentrations, to verify previous determinations.I)2 The capillary-reservoir method was adopted, using experimental procedures similar to those followed by Ma and Swalin,1 with the main exception that radioactive silver was used in the present investigation to facilitate solute-concentration measurements. EXPERIMENTAL PROCEDURE a) 100 ppm Samples. Glass capillary tubes of 2 mm inside diameter and approximately 5 cm- long were sealed at one end, evacuated, and filled with tin of 99.999 pct purity. The region of shrinkage near the mouth was cut off, and the tubes were then placed in a graphite holder and immersed, with the open end up, in an unstirred bath of alloy containing 100 ppm Ag 110, where they remained for periods of up to 30 hr. On removal from the bath they were cooled by an air blower. The bath was kept under a small positive pressure of argon, and the temperature controlled to within +1°C. A 10-hr diffusion period was used in the majority of the tests, scatter on runs of less than 5 hr being rather large. The procedure outlined above was chosen in preference to putting alloy in the capillary and pure tin in the bath, in order to avoid segregation when the tubes filled with alloy were first solidified. To minimize segregation when the diffusion period was complete and the capillaries again solidified, the earlier samples were held in thin-walled silica tubes which could be cooled very rapidly. Later tests were made in precision-bore Pyrex tubes, to eliminate effects caused by variations in the capillary diameter. No consistent differences in diffusivity as measured in the two types of tube were detected. After removal from the glass tubing, the samples were sectioned into 2.5 mm lengths and counted for y activity, using a scintillation counter with fixed geometry. Samples were also drawn directly from the bath and counted, so that values for C/C,, the ratio of the weight of Ag 110 in the sample to that in the bath, could be obtained. b) 5000 ppm Alloy. To check for possible effects of concentration, the silver content of the bath was increased to 5000 ppm. Complete mixing was found to have taken place in the capillary after a 10-hr period at 300°C. It appears that the greater density of the alloy was sufficient for buoyancy forces to cause instability in the alloy-tin interface, leading to rapid convective mixing. For the 5000 ppm alloy, therefore, the bath was of pure tin and the capillary tube was filled with alloy. With this arrangement, values of D consistent with those for the 100 ppm alloy were obtained, Fig. 1. CALCULATIONS OF DIFFUSIVITY The terminology used applies to a capillary of pure tin immersed in a bath of alloy. 1) Error-Function Method. under the present experimental conditions, the rod of liquid tin into which silver is penetrating may be considered semi-infinite. Assuming the concentration at the mouth of the tube to remain constant at Co, the concentration C at distance x from the mouth of the tube at time / is given by3 Plots of the inverse error function of (1 -C/Co) vs .v gave straight lines passing through the origin with slope 1/2-, x being corrected for shrinkage both on solidification and while cooling to the melting point (total correction about 6 pct at 500°C). Values for log D obtained in this manner are shown in Fig. 1. A least-squares fit to the relation D = Do exp(-Q/RT)

Jan 1, 1965

By R. F. Shurtz

R. Duval (Mining Engineer, Ancien eleve de PEcole Polytechnique, Paris, France) I do not agree with the Eq. 3, reading: m =1/100- [(0.214x30.4) + (0.7B6 x0.00)] =6.5pct CaO If 0.214 and0.786 were proportions by weight, the equation would represent the well known mixtures law of the conventional arithmetics and 6. 5 pct CaO would be the correct average content. But it is not the case as the author states: "In samples consisting of single grains of mineral, those grains must, as already mentioned, be either of dolomite or magnesite. Since 78.6 pct of the deposit consists of magnesite and 21.4 pct of dolomite (excluding for present purpose the presence of other minerals), for any single grains picked at random the probability will be 0.214 that is it dolomite and0.786 that is it magnesite. In 1000 such samples the expected numbers of dolomite and mapesite grains will be 214 and 786 respectively." 0.214 and 0.786 would be proportions by weigbt under the necessary condition that all grains of dole mite and magnesite should have an identical weight. Obviously it is not the case, as the specific gravities are not the same for mapesite and dolomite and the volumes of the grains are different. Furthermore, because of these differences the conditions for a random sampling are not fulfilled and we are not authorized to state that the probabilities are, respectively, 0.214 and 0.786. The author however makes a simple application of Eq. 1: M = 1/n— ? fi x i . n Should we deduce that this relation is wrohg? Not at all, but when applying Eq. 1 you must not overlook what it actually. means. Eq. 1 gives a definition of the arithmetic mean of a total of n observed values Xi and nothing else. But the average conteht of a deposit has not the same significance. It is the ratio between the weight of concerned mineral in the deposit and the total weight of the deposit. As from 1000 particles the 214 of dolomite and the 786 of magnesite have not the same weight, the two definitions do not concur, and when applying Eq. 1 the result is an arithmetic mean of figures which has no connection with what is named average contentof a deposit. The situation is similar to the calculation of an average velocity. If a car travels a first mile over at 30 miles per hr and a second mile over at 60 miles per hr, when applying formula 1 you find as average velocity for the 2 miles: 30+60 ------- - 45 miles per hour. Many people calculate in this way and they do not realize that a mistake is involved. In fact the definition of he average velocity for the 2 miles is the quotient of the distance of 2 miles by the time (in hours) necessary for 2 miles travel, i.e.: 2 ---------- = 40 miles per hr. 1 + 1 30 60 In other words, the average volocity wanted is not the arithmetic but the harmonic average of the two velocities. The above mentioned bias in the calculation of the average contents of deposits is frequent, even in the assessments made by experienced engineers and is independant of what is named the sampling error. In order to supress the bias and to be able to use Eq. 1, you must apply a correction. An example on the subject can be found in an article by Duval et al. in the January 1955 issue of the ''Annales des Mines" (French), page 19. R. F. Schurtz (Author's Reply) Mr. Duval's position is quite correct. The proportions shown for dolomite and magnesite., respectively, of 0.214 and 0.786 are, in fact, proportions by weight uncorrected for specific gravity. In our day to day operation of producing magnesite from these mines at a very substantial rate, we do not normally make corrections for the difference between the specific gravity of dolomite and that of magnesite. If these corrections are made in Eq. 3 as shown in my article, then the numbers of grains turn out to be in proportions of 0.226 dolomite and 0.774 mapesite instead of the values actually shown in the equation. For the purposes of our work, and in view of the inherently low accuracy of the data, this correction was not deemed worthwhile making.

Jan 1, 1961