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By R. H. Frazier, F. W. Boulger

THE performance of welded structures is closely associated with the ductile-to-brittle transition temperature of the steel from which they are made. A low transition temperature is desirable because it indicates that the steel is less likely to fail suddenly at low ambient temperatures. Structures such as bridges, ships, storage tanks, and pipelines are usually made from hot rolled semikilled steel. Changes in rolling practice or chemical composition appear to be the most practical methods for improving the toughness of such materials. This results from the fact that production is likely to be seriously curtailed if improvements were obtained by recourse to heat treatment or complete deoxidation. This paper discusses the effect of variations in carbon and manganese contents on the properties of semikilled steels. The transition temperature, a property to which considerable importance is attached, varies with specimen configuration, testing method, and criterion of performance. Both the Navy tear test' and the keyhole Charpy test were used in the investigation. According to the terms used by Vanderbeck and Gensamer,V he tear test was used to measure a fracture transition and the Charpy test to measure a ductility transition. In either case the specimens absorb considerably less breaking energy in tests below the transition temperature than in tests above the transition temperature. Decreasing the testing temperature of notched-bar specimens seems to be equivalent in its effect to increasing the severity of loading on fabricated structures. Therefore, structures built from steels exhibiting lower transition temperatures in laboratory tests are expected to be less susceptible to sudden brittle fractures in service. Consequently, changes in composition which lowered the transition temperature of the experimental steels were judged desirable. Materials and Methods The steels for this study were made in a laboratory induction furnace and rolled to 3/4 in. plate, using a finishing temperature of 1850°F. Precautions taken to insure reproducible melting and testing practices are discussed in detail elsewhere.' All tests were made on hot rolled steels. The analyses of the experimental steels are given in Table I. The list includes steels with manganese contents ranging from 0.21 to 1.46 pct, at each of five carbon levels. The phosphorus, silicon, sulphur, and nitrogen contents of the steels are reasonably constant. The tensile and notched-bar properties of the experimental steels are presented in Table 11. Both upper and lower yield points are listed, and all values are averages for duplicate specimens. Transition temperatures based on three criteria are given. The keyhole Charpy transition temperatures are the temperatures at which the energy-temperature curves based on averages of four specimens cross the 20 and 12 ft-lb levels. Both definitions of Charpy transition temperatures have been used by other investigators. Charpy tests were made at intervals of 10°F, using a pendulum with an available striking energy of 220 ft-lb and a velocity of 18.1 ft per sec. The specimens were oriented parallel to the rolling direction and notched normal to the surface of the plates. The tear test transition temperatures are based on the usual' criterion of the highest temperature at which at least one of four specimens exhibits brittle behavior. The dimensions of the tear test specimens are shown in Fig. 1. The specimen is loaded eccentrically in tension, with pin and shackle fixtures, through the large holes while submerged in a liquid bath at the proper temperature. A specimen developing a fracture area with less than 50 pct shear or ductile texture is classed as brittle. Tear tests were made at intervals of 10°F.

Jan 1, 1955

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By J. E. Spruiell, F. H. Patterson, B. F. Shuler

The microstructures and textures developed by the working of high-purzly thermochemically deposited tungstem sheet have been inuesligated. Greater than 60 pct reduction was required to deslroy the columnar grain structure which existed in the as-deposited sheet. With increasing reductions the texture gradu-ally charged from the initial as-deposited orientation with (100) parallel to the sheet normal to a (100}(011) ideal ovienlation with some spread about the rolling direction. This texture was retained after recrystalli-zation a1 2000°C. THE processes for depositing tungsten by hydrogen reduction of tungsten hexafluoride have been under development for the past several years.1,2 The nature of the deposition process is such that the as-deposited material contains a highly oriented columnar grain structure perpendicular to the deposition substrate. This well-defined columnar structure may be useful in certain applications293 but a wrought or equiaxed structure may be desired for some components such as tubing. Knowledge of the effects of working ther-mochemically deposited (TCD) tungsten is therefore necessary in order to establish the feasibility of obtaining worked and recrystallized microstructures and textures. The details of a recently developed technique for thermochemically depositing flat, uniformly thick tungsten sheet are presented with emphasis on the effects of deformation by rolling on the microstructure and texture. Although no work has been previously reported on the rolling and the annealing textures of TCD tungsten, there have been some determinations of textures for cold-rolled tungsten foil prepared from powder-metal -lurgy billets.4-8 The general description is that of a predominantly lurgy{100}(011) texture, with some spread about the rolling direction as an axis. pugh5 reports data both for cold-rolled and for annealed foil having about 96 pct initial cold work. He observed no change in texture, except for a decrease in the spread, for annealing treatments of 30 min at temperatures up to 1800°C. On annealing at 1900°C, both the low-temperature components plus new components which were described alternately as {001}(320) plus {001)(230) or as {100}(011) ± 12 deg about the sheet normal were observed. Above 1900°C, the new orientation existed alone, and it was stable up to 2500°C, the highest temperature that Pugh investigated. THERMOCHEMICAL DEPOSITION OF TUNGSTEN SHEET High-purity tungsten sheet was reproducibly deposited on the inner walls of a molybdenum mandrel by the thermochemical reaction WFs(g) + 3H2(g) - W(s) + 6HF(g). The mandrel was heated by a five-zone tube furnace which afforded a controllable fixed-temperature profile. Sheets measuring 1+ by 12 in. have been deposited with uniform thicknesses of up to 0.145 m. As shown schematically in Fig. 1, the purified reaction gases were metered into a mixing chamber at a Hz-to-WF6 ratio of 15 and preheated to 350°C. The flow rate of the WF6 was 300 cu cm per min at stp. These gases were directed through a conical injector into the deposition chamber. Inside this chamber hydrogen reduction of the WF6 to pure tungsten metal occurred on the hot walls of the molybdenum mandrel at a total pressure of 5 Torr. Typical temperatures for the five zones in the chamber were, respectively, 565", 540", 550°, 570°, and 590°C. The hydrogen fluorlde generated from the reaction, the excess hydrogen, and some un-reacted WF6 were pumped on through the scavenger

Jan 1, 1968

By A. D. LeClaire

This paper claims to provide a description of diffusion processes in solids which is said to be a reformulation of Fick's Laws and therefore, presumably, is supposed to be as general as those laws. In fact, it appears to provide no more than an atomic model of a rather restricted type leading even to results in conflict with experiment. The restriction lies in the assumption, carried throughout the paper, that even in a chemical gradient the jump frequency i of an atom of species i is a function only of the composition on the plane from which it jumps, i.e., ?i = ?i(cl, c2 ...). This means that atom jumps in opposite directions from a site would occur with equal probability. There would then be no tendency for atoms to migrate preferentially in one direction along the gradient, so the model is incapable of accommodating the well established phenomenon of atom drift in a chemical gradient.10-" A more general model that does not suffer this difficulty was discussed in a paper13 I wrote in 1958, and the results therein already contain as a special case those given by Dr. DeHoff. The simplest sufficiently general assumption is to suppose that ?i is a function ?i(a1 a2,...; wl, w2, ..-) of the concentration aj and ? ?j at the site from which and to which, respectively, a jump is made. Any such function can always be expressed as a function of the sum and difference of its arguments. Thus d is the jump distance and g a geometrical constant. Obviously this is zero, i.e., no drift, if ??ri/??j = 0. X is written in this form, revealing two components of the total drift, because it can be shown that only the second component, depending on ??'i/???(?j -aj), actually contributes to the net diffusion flux Ji. This component can be shown,13 by a straightforward ther-modynamic transcription, to be responsible for the so called "thermodynamic factor" in the Darken approximation for a chemical diffusion coefficient is the activity coefficient of i. Because the jump rate ?i in DeHoff's approximation has no dependence on the concentration gradient it does not seem possible to derive the Darken equation from his Eq. [6] without the further rather arbitrary assumption that ?i = const ri. It is to be noted too that the author's derivation of Eq. [12] is only valid when ?i is in fact a function only of the cj at the plane from which the atom jumps—for only then is ci?i a unique function of position and therefore of A. Author's Reply R. T. DeHoff I am indebted to Dr. LeClaire for his penetrating discussion of my paper, "A Reformulation of Fick's First Law". I concede that it does appear initially that the relationship presented in my paper could be derived from the detail atomic model of random walk and atom drift presented in Dr. LeClaire's approach. However, there are some important differences in concept and viewpoint which deserve further amplification. Dr. LeClaire's description is penetrating, detailed, and fundamental. His approach describes an extremely complex phenomenon, the displacement of atoms in a multicomponent gradient, at a sophisticated level. For precisely these reasons, his analysis has not proved to be useful for experimental studies that have practical objectives. For example, in order to obtain the information required to complete the analysis of the jump frequency distribution in a ternary system, the following series of experiments would, I believe, be required: 1) chemical (gradient) experiments, covering the composition range;

Jan 1, 1970

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

By C. W. Price, G. A. Wheeler

BERYLLIUM has always been a difficult material to prepare for metallographic examination. Severe surface deformation occurs during mechanical grinding and polishing, and a suitable bright-field etchant has not been developed. Certain electrolytic techniques produce satisfactory polishes, but these techniques have not yielded entirely consistent results. Furthermore, they have not provided satisfactory bright-field etches. The purpose of this paper is to describe an electrolytic polishing technique that can also provide an excellent bright-field etch. In addition to the bright-field etch, other advantages of this technique are excellent reproducibility, rapidity, and ease of polishing and etching. Experimental Technique. Specimen Preparation. Beryllium specimens may be either mounted or unmounted for the use of this technique, and the size of the specimens is not important. Specimens with surface areas up to 4 sq cm have been electrolytically polished and etched successfully with this technique. The most important requirement is to provide a good electrical contact to the specimens, preferably on the back of the specimens. When specimens are mounted, a hole is drilled through the back of the mount so that the specimen can be contacted with a probe. Conventional metallographic grinding techniques are used to prepare the specimens for electrolytic polishing. The specimens are ground on silicon carbide papers. Grinding through the usual series of papers down to the 600-grit paper is recommended to minimize the electropolishing time, although successful electrolytic polishes and etches have been obtained by grinding only through the coarser papers. A continuous flow of water is used during grinding to provide lubrication and to minimize contamination. Mechanical polishing is not required because high rates of material removal are achieved with the electrolytic polishing. Polishing. Most of the results reported in this paper were obtained with a "Disa-Electropol", manufactured by Struers Scientific Instruments of Copenhagen, Denmark. Satisfactory results have also been obtained with the conventional beaker technique of electrolytic polishing, however, the conditions applicable to both the Disa unit and the beaker technique will be described. Stainless-steel cathodes are used in both techniques. In the beaker technique, a flat cathode, with an area at least twice that of the specimen, is used, and the specimen is held parallel to the cathode. The distance between the specimen and the cathode affects the quality of the electropolish. This distance is set at about 7 mm in the Disa unit; the same distance produces the best results in the beaker technique. Specimen-cathode distances greater than about 20 mm produce considerable relief, while distances less than 7 mm cause high current densities that are difficult to control. An electrolyte of 2 pct HC1, 2 pct HNO3, and 2 pct HCIOl in ethylene glycol gives the most satisfactory results for both electrolytic polishing and etching. This electrolyte was developed by altering the composition of a similar electrolyte used for electrolytic lapping1 and adding HClOl to improve the etching characteristics of the electrolyte. Variations of from 0.25 pct to as much as 5 pct of each of the acids do not significantly affect the results, but the greatest amount of control and reproducibility can be obtained with the composition of 2 pct of each acid. Generally, lesser amounts of the acids produce lower polishing and etching rates, while greater amounts of acids cause high current densities that are difficult to control.

Jan 1, 1968

By D. W. Frommer, M. M. Fine

Mineral dressing research showed that iron concentrates of commercial quality could be produced from the Pea Ridge deposit near Sullivan, Mo. Magnetic separation and flotation, on a laboratory scale, yielded concentrates ranging from 60.0 to 71.4 pet Fe at recoveries of 89.9 to 97.6 pct. Early in 1957 St. Joseph Lead Co. announced discovery of three new centers of iron ore deposition in east central Missouri.' The discovery resulted from exploratory drilling in the vicinity of a magnetic anomaly or high. A deep hole, drilled into the Pre-Cambrian porphyry to determine the cause of anomaly, penetrated a magnetite-rich deposit.' The magnetic surveys that revealed the anomalies were begun by the Missouri Geological Survey in 1929 and were continued into the 1930's.3 At that time an area in Crawford County known as the Bourbon magnetic high was located. A second anomaly, similar in size and intensity, was discovered about six miles to the northeast in Franklin County in the vicinity of Sullivan. This area was not studied in detail until the early 1940's. To determine the cause of the anomalies, the USBM drilled four holes at the Bourbon site in 1943-1944.4 The most productive hole penetrated four mineralized zones having a total thickness of 127.5 ft. These zones contained magnetite in rhyo-lite porphyry at depths between 1600 and 2000 ft. Additional iron ore below 2000 ft was considered a possibility at the time. Some years later, the USGS, Missouri Geological Survey, St. Joseph Lead Co., and others cooperated in sponsoring an aeromagnetic survey of the Bourbon-Sullivan area which resulted in discovery of a third high, about eight miles distant at Pea Ridge. This deposit, with an estimated reserve of 50 to 100 million tons of iron ore, is considered the main find, although other orebodies in the same general area are of definite interest.' When this discovery was announced, St. Joseph Lead also revealed plans to exploit the deposit jointly with Bethlehem Steel Co. A new corporation, Meramec Mining Co., was established, and 1962 was set as the target date for completing physical plant.2 Annual production goals of 2 million tons of beneficiated and pelletized iron ore were proposed. Preparation of the site for shaft sinking was begun in June 1957. Orebody and Character of Samples: Drilling to date has established the Pea Ridge orebody as a crescent-shaped pipe about 300 ft wide. Some drillholes were bottomed at 2800 ft in very good iron ore.6 he orebody is predominantly magnetite, although hematite and a mixture of hematite and magnetite occur in the upper areas and peripheral walls. Drillhole cores representing ore from different areas and depths of mineralization were grouped into composites for testing. These composites consisted of: 1) medium grade mixed hematite and magnetite, 2) high grade mixed hematite and magnetite, and 3) high grade magnetite. The medium grade ore came from three holes with depths of i350 to 1900 ft. The high grade mixed hematite and magnetite cores came from the 1790 to 2812-ft interval of one hole. Partial chemical analyses of the three samples, given in Table 1, reveal that all are excessively high in phosphorus and sulfur, and sample 1 is

Jan 1, 1960

By L. H. Wolfe, J. O. Thieme

The tensile and shear strengths of frozen soil and the compressive strengths of ice and frozen soil were measured These tests showed that the strength of ice and of frozen soil increased as the temperature was decreased. A method is presented for the measurement of thermal conductivity and specific heat of earth and ice. Using the parameters thermal conductivity, specific heat and density, the thermal diffusivity was calculated. Results of thermal property tests establish water as the major variable contributing to thermal property values. INTRODUCTION During the last few years, a considerable interest has developed in underground storage of cryogenic liquids such as liquid natural gas. Because of its economy and safety, underground storage is being used. Before underground caverns could be seriously considered, however, the strength and thermal characteristics of the soil had to be obtained. Methods are presented herein for measuring tensile, compressive and shear strengths, specific heats and thermal conductivities. The tests were performed on two soils at temperatures from ambient to -195C. Because it is difficult to find data in the literature that pertain to a particular soil, ice was used to evaluate some of the experimental procedures. Some of our ice data are compared to the published values. PHYSICAI, PROPERTIES SOIL SELECTION AND SAMPLE PREPARATIONS The physical and thermal tests were performed on recompacted samples of two typical soils that might be encountered in underground caverns: a gray, fire clay that had been pulverized and mixed with water into a pliable mud; and a brown, sandy silt that was dug from a dry river bank and subsequent1y mixed with tap water. The moisture content of the test specimens was 17 to 22 per cent (based on the wet weight of the soil). This amount of water nearly saturated the silt, but the clay was well below the saturation point. The soils are partially described by the sieve analyses (Fig. 1) which show the particle size distribution of the coarser than 44 micron portion of the soils. The curves also show that approximately 75 per cent of the clay and 20 per cent of the silt are finer than 44 microns. The particle size seems to affect some of the physical properties, and the finer than 44 micron portion is important in the thermal conductivity test. Physical specimens were cut with a bandsaw from frozen blocks of the soil. The specimens were then sanded and kept frozen until after they were tested. They were stored at the approximate test temperature for several hours. Then, to equilibrate the samples to the test temperature, they were stored at the temperature at least an hour before they were tested. TEST EQUIPMENT An Instron, which is a constant speed gear-driven instrument, applied force to the samples and drew stress-strain plots of the test. All of the samples were strained at 0.02 in./min. All of the physical tests were conducted in a temperature cabinet that controlled the temperature to 1C. TENSILE STRENGTH Briquette or "dog-bone" shaped tensile specimens were pulled with suitably shaped jaws. This shape of specimen, which is usually used for tensile tests of concrete, is satisfactory for testing frozen soils except that the samples tend to

Jan 1, 1965

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

By R. G. Powell, R. Schuhmann, E. J. Michal

Liquidus surfaces in the ternary system FeO-Fe2O3-SiO2, were determined from 1250' to 1450°C by the procedure of equilibrating small samples in platinum crucibles, quenching, and microscopic examination. The experimental results were combined with previously published information to construct a ternary diagram for the system showing the entire temperature-composition range of stability of iron silicate slags. Metallurgical applications of the diagram, especially in copper smelting, are discussed briefly. IRON oxides are almost unique among the common oxide constituents of metallurgical slags in that the iron occurs in two different states of oxidation, ferrous and ferric. Moreover, in liquid slags the degree of oxidation of the iron is readily changed by reactions of the slags with oxidizing agents or reducing agents. This behavior of iron oxides in slags accounts, for example, for the effective transfer of large quantities of oxygen through slag layers in open hearth steelmaking. In this process, oxygen supplied by reactions at the gas-slag interface is dissolved in the slag with the oxidation of ferrous iron to ferric. Ferric oxide is transported across the slag layer by convection, and at the slag-metal interface the oxygen reacts with liquid metal while the ferric iron is reduced back to the ferrous state. Another group of processes in which variation in degree of oxidation of iron has great practical importance is in copper smelting. In matte smelting and converting, such large proportions of the iron are oxidized to the ferric state that problems are encountered in preventing or controlling the formation of solid magnetite. The ferrous-ferric relationship also affects the attack of iron oxides on high-SiO2 refractories, which appears to be most severe under reducing conditions for which ferrous iron predominates. Darken and Gurry' determined the chemical properties and phase equilibria of pure iron oxide slags. Their data show that iron oxide melts can have compositions ranging almost all the way from FeO to Fe2O3. The melts of lowest oxygen contents, which exist in equilibrium with metallic iron, approach ferrous oxide in composition but still have a small percentage of ferric oxide. The melts of highest oxygen contents, which have oxygen dissociation pressures of 1 atm, are above magnetite in oxygen content, with over two-thirds of the iron in the ferric state. The previously established phase diagrams for silicate slag systems all show FeO as the iron oxide component. However, Bowen and Schairer? who determined the FeO-SiO2 diagram and many of the other diagrams used by slag chemists, have been careful to point out that their systems always contained both ferrous and ferric iron. Thus, their data are for limiting mixtures with minimum contents of ferric iron, obtained by melting and equilibration in iron crucibles. Under these conditions, the Fe2O3 percentages found by analysis were small enough to justify simplification of the published phase diagrams by calculating the Fe2O3 to equivalent FeO and ignoring Fe2O3 as an additional component. On the basis of experimental measurements of melting points of iron oxides on silica in the presence of various gas mixtures, Darken3 worked out phase diagrams for the Fe-Si-0 system which show the important phase equilibria in terms of temperature and gas composition. This study clarified many aspects of the application of the phase rule to the FeO-Fe2Oa-SiO2 system and was an important basing

Jan 1, 1954

By J. B. Scott, J. L. Popham, H. F. Coffer, J. J. Reynolds

This paper concerns field experiments to define the areal extent, orientation and thickness of an artificial fracture in the Sacatosa field, Maverick County, Tex. The fracture was made by a sand-oil treatment of 176,-000 gal of lease crude containing a fluid-loss additive and 270,000 lb of 20-40 mesh subangular Poteet sand. The well was perforated with a jet gun, consisting of six shots in a single plane. Fourteen test holes were drilled at various locations around the fractured well. Drill-stem tests, Micro and Sonic Logs, coring and sampling of formation cuttings were used to determine the presence of the fracture in these holes. The test holes were drilled at distances up to 250 ft in a radial pattern around the fractured well. In addition to fracture areal extent and orientation, sand grain size before and after fracturing, erosion of perforations and fracture thickness were studied. INTRODUCTION The orientation,12 areal extent3, 4 and thickness5-9 of artificially induced fractures in reservoir rock by hydraulic means have been discussed in great detail in the oil industry in recent years. Methods for initiating vertical"' and horizontal" fractures have been tested in the laboratory and the field. Although the methods used give successful well stimulation, good field data on the physical characteristics of the fracture are lacking in the literature. It is recognized generally that properties of a fracture, such as thickness, sand placement in the fracture" and shape, may vary from reservoir to reservoir. This paper gives data on size, orientation and sand placement in a large fracture initiated in a single plane in Sacatosa field, Maverick County, Tex. It is not intended as a speculative study; rather, it is restricted to actual field data on fracture properties. No attempt is made to prove that the same type of fracture occurs in all wells. The field procedure was to drill 14 test holes at various locations around the fractured well. By employing several different testing techniques, the presence of the fracture and some of its characteristics were determined. These techniques as well as the results obtained are discussed in detail in this paper. DESCRIPTION OF FRACTURE TREATMENT N. J. Chittim Well No. 37-1, completed in the San Miguel No. 1 sand, Sacatosa field, Maverick County, Tex., was chosen for the field study. The San Miguel sand is a tight, well consolidated sandstone with an average porosity of 23 per cent. The permeability ranges from 0.1 to 10 md, with a median permeability of 2.3 md. The sand thickness averages 23 ft and is located at depths of 1,150 to 1,700 ft throughout the field.I3 The fracture treatment performed on Well 37-1 was as follows. 1. The well was drilled to a depth of 1,438 ft with native mud, and 51/2-in. casing was set and cemented to the surface. 2. The casing was perforated at 1,349 ft with a fracture-initiating jet gun. This gun consists of six shots, 7/16-in. diameter in a single horizontal plane. The jets were oriented in two groups of three, 180" opposed. The perforating device was designed to initiate a fracture perpendicular to the wellbore.

By C. E. Violet, R. J. Borg, E. M. Howard

The miscibility gap in the Au-Ni system has been determined by Mossbauer spectroscopy, with used as a probe. The phase boundaries were determined from the compositional dependence of both the isomer shift and Curie temperature. X-ray diffraction measurements were also used to confirm the Mossbauer results. 1 HE purpose of this research is to demonstrate the application of Mbssbauer spectroscopy to the determination of phase boundaries and to redetermine the miscibility gap by an independent and novel technique. The techniques evolved in this study are readily applicable to other polyphase systems and are generally as quick and accurate as the more conventional methods, e.g., metallography, X-ray diffraction, thermal analysis, and so forth. To be sure, not all polyphase systems will lend themselves favorably to Mijssbauer investigations, but this is a problem met in the use of conventional methods as well. The Mbssbauer spectrum responds to a different set of physical parameters, and consequently provides an entirely independent method of analysis. It is especially useful if the system has either a ferromagnetic or an antiferromagnetic transition. The Au-Ni system was selected because alloys containing more than -60 at. pct Ni become magnetically ordered at low temperatures; also the miscibility gap is quite well established (see Ref. 7 for a compilation of pertinent references, also Fig. 11, and thus provides a reliable test of this novel procedure. As Fe is the most commonly used Mijssbauer isotope, there exists a wealth of information concerning its behavior in iron-containing alloys and compounds. However, as yet there have been relatively few experiments using it as a probe to investigate nonferrous systems. By choosing a nonferrous alloy system, we are able to demonstrate that its use is not restricted to systems containing iron as one of the major constituents. Wertheim and ~ernick' have used the same method to investigate Cu-Ni, and demonstrated that one can obtain a systematic variation in the isomer shift and magnetic hyperfine field. However, we believe this to be the first time these techniques have been used to establish phase boundaries. Two hyperfine interactions were measured and used to determine the phase boundaries, viz., the magnetic hyperfine splitting and the isomer shift which in this alloy system are both strong functions of composition. Calibration curves were established based upon single-phase solid solutions obtained by quenching from temperatures well above the maximum of the miscibility gap, see Fig. 1. Solid solutions containing 25, 50, 65, 75, 85, 92, and 96 pct Ni as well as pure nickel were used in the calibration procedure. Fig. 2 shows the Curie temperature, TC, and the isomer shift, v,, as determined from the Mbssbauer spectra, and variation in lattice parameter as determined by X-ray diffraction, as functions of composition. The compositions of the two-phase systems quenched from temperatures within the miscibility gap are obtained by comparing their respective values of TC and v0 with the calibration data. I) EXPERIMENTAL Mbssbauer sources were made by fusing the component metals in a tungsten arc melter, which has a water-cooled copper hearth. Both nickel and gold were 99.999 pct pure, and the melting was done in an atmosphere of purified argon. The alloys were rolled, diced,

Jan 1, 1969

By Henry P. Chandler

Tripoli is the general name for a number of fine-grained, lightweight, friable, minutely porous, forms of decomposed siliceous rock, probably derived from siliceous limestones or calcareous cherts. Tripoli is often confused, both in the trade and technical literature, with tripolite, a diatomaceous earth (diatomite), found in Tripoli, North Africa. A material found near Seneca, Mo., resembling tripolite was incorrectly termed "tripoli." This name has persisted and now has a definite physical and trade meaning. However, tripoli contains no diatoms, is of an entirely different origin, and has chemical and physical properties different from those of tripolite. There are two distinct types of tripoli in the United States; that from the Missouri-Oklahoma field and that from the Southern Illinois field. Commercially the term "tripoli" is applied to the material from the Missouri-Oklahoma field, while the material from the Southern Illinois area is often referred to as "amorphous" or "soft" silica. Material similar to the Missouri-Oklahoma tripoli, but finer grained, occurs in northwestern Arkansas. In its Minerals Yearbook the Federal Bureau of Mines groups statistically under "natural silica abrasives," tripoli from these producing areas and rottenstone from Pennsylvania. The justification for this grouping is the similarity of use. Composition and Physical Properties Commercial tripoli contains 97 to 99 pet SiO2. The remainder is mostly alumina, iron, lime, soda, and potash, some of which may impart desirable physical properties to the material. Variations in the chemical composition of tripoli are not as important as its physical characteristics. The color of tripoli varies from white to cream, brown, rose, and red, the variations from white being the result of iron deposited from percolating surface waters. The commercial varieties of tripoli mined in the Missouri-Oklahoma area are designated as cream and rose. Other physical properties of the tripoli from this area are: Free quartz, less than 0.5 pct; oil absorption, 50.71 to 53.14 pct; water absorption of the crude tripoli, about 38 pct, and of prepared material, about 52 pct; fracture, uneven to conchoidal; specific gravity, 2.15 to 2.62; weight per cubic foot crude, 35 lb, ground, 55 lb; fusion point, 3,225° to 3,300°F; and refractive index, 1.54. Tripoli occupies about 1 cu yd to the short ton in place and about 1.5 cu yd when broken. Packed for shipment, the powdered material occupies about 33 cu ft to the ton. Its value and usefulness depend primarily on a low content of crystalline silica, size of the natural particles, absorption, and color. Some beds in the Missouri-Oklahoma area are of sufficiently compact material that large, fairly strong blocks may be removed. These find a market as filter blocks and have been used for building material. In the Southern Illinois field the color of the material is the important physical property; pure white is preferred. The rottenstone mined in Pennsylvania is of higher density and lower in silica content than the various types of tripoli. Its composition approximates 60 pct silica, 18 pct alumina, 9 pct iron oxide, 8 pct alkalies, with small amounts of lime and magnesia. The material apparently is a ferruginous and siliceous shale, having properties rendering it suitable as an abrasive or as a filter for paint, rubber, and plastics.

Jan 1, 1960

By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By W. D. Brown

Newell1 has shown that hydrogen is removed from steel in a vacuum at a temperature of 500° to 900° C. within 136 hr. Holm and Thompson2 also state that, especially when the hydrogen is high, the results obtained by extraction at 800°C. agree with those obtained by vacuum fusion. In this laboratory, an apparatus was designed (Oct. 1940) and used wherein the piece of steel was heated at 100°F. in a Torricellian vacuum (Fig. I). This vacuum was produced by raising and lowering a "leveling bottle or bulb" containing mercury. Extensive tests were made with this apparatus. The weakness of the procedure was the possibility of leakage of air into the tube around the rubber stopper at the bottom. The present plan is to raise and lower the mercury by applying vacuum from a mechanical pump, to the top of the tube and then to a bottle of mercury in which the bottom of the tube is immersed. The Apparatus The extraction is made in a Pyrex tube A, I in. i.d. It is drawn down at the top at N and an 8-mm. i.d. tube is welded on it. To this a Pyrex stopcock E, 4-mm. bore, is welded. The tube between N and E is preferably 8 in. long and is graduated in milliliters. The total length of A to the stopcock is 28 inches. Heat is supplied by a split-tube furnace. 0 in. long by 6 in. in diameter, hinged on the side. A short pyrometer couple P is inserted through the walls of the furnace. In use this is standardized by comparison with a standard couple in a I-in. tube, just opposite this short couple. In the I-in. tube A a glass rod R, flattened at one end, supports the sample S and the length of R is so adjusted that the sample is in proper place. (It may float in the mercury.) The tube A is inserted in a large rubber stopper to fit the bottle B and extends nearly to the bottom. It is so placed that the handle of the stopcock faces the operator. In this stopper also is a short tube D bent at right angles for the application of vacuum. Also in this stopper is an 8-mm. tube C reaching nearly to the bottom; this is bent so as to miss the heater and again bent to bring it in line with and as near as possible to the upper and reduced part of tube A. On this tube C is welded a 4-mm.-bore stopcock H. In order that the two tubes may be as near as possible, the handle of stopcock H faces the back, or is the reverse of stopcock E. The total height of II above the bottom is 28 in. As explained later, this is the pressure-measuring tube C. The bottle B is about half full of mercury. The mercury must cover the ends of A and C by about I in. when they are evacuated. By tees T and rubber tubing RT the tubes A, C and D, the latter through the three-way stopcock M, are connected to the vacuum pump. A sheet of asbestos at K prevents the stopcocks E and H from becoming so hot that they leak. A good grade of vacuum lubricant prevents leakage of E and H. In order to measure the pressure of the

Jan 1, 1945

By L. C. Armstrong

Twice in the past two years and in two widely separated localities—ane near Williamsville, Mo., and the other in the Allard Lake district of Quebec— the Contract Drilling Division of the Longyear Company has experienced perplexing difficulties in drilling granitoid igneous rocks. The rocks in both places are characterized by appreciable amounts of feldspar intimately inter-grown with quartz particles of microscopic dimensions. The disappointingly slow rate of advance and the exceptionally high bortz loss, obtaining during the life of these two projects, are ascribed largely to the resistance to abrasion of these two minerals when arranged in this intergrown pattern. Whether all intergrowth-bearing igneous rocks would offer extraordinary resistance to bit progress cannot be stated with assurance on the strength of these experiences alone. More data on diamond drilling this sort of material in a number of localities are needed before any generalizations can be made safely. It should be pointed out that the lack of time and funds made it impossible for the writer, or other persons interested in correlating the details of bit histories with the kinds of rocks drilled, to be present during the performance of the contracts. However, the records kept in the normal course of drilling are deemed complete enough to be reportworthy. This information is presented here together with the findings made in studies of the rocks involved, with the thought that it may attract the comments of others who may have encountered similar refractory drilling conditions. A pooling of knowledge on the problem would be of material aid in devising more efficient cutting tools and procedures for penetrating this kind of rock. Drilling Blastholes in the Williamsville Granite Due to the unsatisfactory perform- ance of pneumatic percussion drills in boring blastholes on a construction contract near Williamsville, Mo., tests were made with a diamond drill. The poor progress achieved and the excessive loss of diamonds, however, soon led to the abandonment of these trials. The diamonds, in all of the bits tried, lost their cutting edges and acquired a polish after being in service for distances ranging from a few inches to a few feet. Coring bits containing surface-set, whole-stone bortz in a tungsten powder matrix were employed. The cost assignable to bortz wear averaged $7.17 per foot. This item of expense is several times the amount normally expended in diamond drilling in firm, unfractured, granitic rocks. Diamond-impregnated, tungsten carbide bits also were used without success. The diamond wear was at the rate of $0.98 per foot, but the diamond chips became too polished for further duty in less than a foot of drilling. The Williamsville granite is pink and medium-grained. In the hand specimen, it has a fresh, sound appearance; it is seemingly composed almost entirely of interlocking grains of feldspar and quartz and has no discernible features suggesting a greater durability than is usually found in rocks with this composition and texture. Microscopic examination, however, reveals a predominance of feldspar grains with more or less regularly distributed and sharply angular masses of quartz (see Fig 1). The pattern assumed by the two minerals in this mode of occurrence is referred to as a "graphic intergrowth," as it bears some resemblance to the cuneiform characters of ancient Persian writing. The other principal constituents are quartz-free feldspars (microcline and orthoclase) and quartz. All of these constituents are in nearly equidimensional grains, ranging up to about 3 mm in length. There are also

Jan 1, 1950

By S. J. Rothman, L. T. Lloyd

S. J. Rothman and L. T. Lloyd (Argonne National Laboratory)— Hagel's paperz0 discusses the question of the mechanism for self-diffusion in bcc transition metals. Recent work21"23 has led us to agree with him in reabandoning the ring mechanism in favor of a defect mechanism, most likely vacancies. On the other hand, we think that Hagel's attempt to group together all self-diffusion in bcc transition metals is wrong. We prefer the scheme of Peart, Graham, and omlin," who separate them into two groups. One group contains the anomalously behaved metals P titanium,', y uranium, and perhaps zirconim.' The other group contains a iron," this alloy was held at 1800°C for 2 hr before quenching, its structure was all a. B. C. Giessen, I. Rump, and N. J. Grant (Authors' reply)—We very much appreciate the discussion by Deardorff and Kato regarding the a to /3 transformation temperature of hafnium. In the W-Hf program, as well as in a current study of the system Cr-Hf, standard precautions were exercised against contamination, including vacua of less than 10"5 mm Hg and a weight control check of all specimens to insure an impurity rise of less than 100 ppm. Following receipt of the above discussion, a revision was made in the annealing process. Arc-cast specimens were etched with a 10 pct HF-90 pct HNO solution until 1 mm of surface, including a possible oxide film, was removed. Annealing was done in a hafnium container which provided a long diffusion path for gaseous contaminants. Finally, the heat treating time was shortened. Structural changes were noted to occur quite slowly. A 99.5 at. pct Hf alloy showed 70 pct /3 after 30 min at 1700°C and was 100 pct /3 after 10 min at 1715°C. After 24 hr at 1740C, the alloy was found to be 10 pct/3. This change is due to contamination; it was estimated that it corresponds to an increase of 60°C in the transformation temperature over a 24 hr period. The corresponding change in 30 rnin would be slight. Using the same hafnium as in the above publication, and three new alloys at 98, 99, and 99.5 at. pct Hf, the transformation temperature was indicated to be 1715" 15°C. Since this hafnium contained 4.4 at. pct Zr, a correction of 40 5C, based on an assumed approximately linear transformation temperature curve, must be made for pure hafnium. This yields a value of 1755 20°C in good agreement with Deardorff and Kato's value. Because the slope of the boundary is small, this permits a good extrapolation, and we regard the W-Hf alloys as well suited to check the Hf transformation temperature. niobirn,'' and molybdenum,22 whose activation energies correlate with the melting temperature and whose Do values follow Zener's predictions.28 We have no quarrel with Hagel's placing chromium into the second group; we disagree with his interpreting our data to make uranium fit into that group. Hagel considers that the measurements of self-diffusion in uranium below about 950°C represent combined volume and grain boundary diffusion. This contention is based on the curvature of the penetration plot for our 891°C run,4 which also has a nearly straight line plot of log c vs x. Hagel has extrapolated these characteristics to our 803.5C run and fitted his Arrhenius plot for self-diffusion in y uranium to our four highest temperature points only. We think this is wrong for the following reasons.

Jan 1, 1963

By S. C. Sun

With the aid of emulsifiers, intense high-frequency sound waves are capable of emulsifying any collector in water. The data show also that ultrasonically emulsified collectors are more effective in floating minerals than the nonemulsified collectors. THE use of ultrasonics in forming emulsions is not new. As early as 1927 Wood and Loomis reported preparation of emulsions with ultrasonics. In 1935 Rschevkin and OstrawskyV escribed the use of great ultrasonic power in producing fine emulsions of various oils and paraffin in water. Recently Oyama and Tanaka3 employed ultra-emulsification to increase the effectiveness of sodium ethyl xanthate in flotation of chalcopyrite and galena. An emulsion is a two-phase system consisting of two incompletely miscible liquids, the one being dispersed as finite droplets In the other. The dispersed liquld is known as the internal or discontinuous phase, and the surrounding liquid is termed the external or continuous phase. There are two types of emulsions; one is oil-in-water (O/W) and the other water-in-oil (W/O). The word oil refers to the liquid other than water. Circumstances exist in which the emulsion type is not clearly defined, and the internal and external phases both contain portions of the opposite phase. This is said to be a dual emulsion. Among the many hypotheses, 5a, B proposed for the formation of emulsions, the Bancroft's adsorbed film or double interfacial tension theory is widely accepted. Bancroft 7, 8 deduced that in the process of emulsification the interfacial tension between oil and water is lowered by the formation of an emulsifying film, which contains the adsorbed molecules and/or ions from the emulsifying agent and the two liquids. This film has two interfacial tensions, one with the water and the other with the oil, which are not necessarily equal. The difference in interfacial tension between the two surfaces of the film is chiefly responsible for forming different types of emulsions. For example, if the interfacial tension between water and film is less than that between oil and film, the film will become convex on the water side, thereby tending to form an oil-in-water emulsion. On the other hand, if the interfacial tension between water and film is greater than that between oil and film, the film will become concave on the water side, thereby tending to make a water-in-oil emulsion. In line with this theory, emulsifying agents soluble in water have the tendency to form oil-in-water emulsions, while those soluble in oil form emulsions of the reverse type. Apparatus and Experimental Procedure: The ultrasonic apparatus shown in Fig. 1 consisted of a hypersonic generator (A), Brush Development Co. model Bu-204; a hypersonic transducer bowl (B) whose resonant frequency is 400 kc per sec; and a round-bottomed glass tube (C) of 2.2 cm ID and 21 cm in length. The acoustical output power of the hypersonic transducer bowl was standardized with a Hewlett Packard vacuum tube voltmeter, model 41 0B, across the hypersonic generator output. The glass tube, containing the materials to be emulsified, was placed 1 cm above the central surface of the transducer bowl, which was filled with water as shown in Fig. 2. Ultrasonic emulsification was performed in three steps, although a one-step method has been used: 1) emulsifying the predetermined amounts of col-

Jan 1, 1956

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and "{2,3,10)" or "(127)". (It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove.' The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and tj2 = vi (i = 1, 2, 3), the Kz qd 771 elements are given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics cij Iand cij reduce to the unit tensors 6ij and 6ij so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and 77~ are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By S. J. Rothman, J. J. Hines, D. Rokop, R. Bastar

Self-diffusion has been measured along each principal axis of mosaic-structured and relatively perfect a uvaniuln single crystals. The anisotropy reported before,' D[loo] = D[001] » D[010 , has been confirmed. and is shown to represent volume diffusion. Diffusion along the dislocations in the imperfect crystals increases the measured value of D significantly without changingr either the shapes of the penetvation plots or the anisotropy. SINCE a uranium is orthorhombic, the diffusion coefficients along the principal crystallographic axes need not be equal. A previous measurement of self-diffusion in three mosaic-structured a uranium single crystals1 showed that Dil00| =D[001 >>D[010 This result was deduced from penetration plots similar to those in Fig. 1. That is, the plots for diffusion along [loo] and [001] were the straight lines expected from the solution of the diffusion equation for the boundary and initial conditions of the experiment, while the plot for diffusion along [010] was curved so that the part near X = 0 had a much steeper slope than the straight lines did. The observed anisotropy could have been due either to volume diffusion or to diffusion along the very large number of dislocations in such crystals, according to the model proposed by aart.' The authors of Ref. 1 argued that the latter possibility was unlikely, but did not exclude it. To settle the question, a simultaneous measurement of self-diffusion in mosaic-structured and mosaic-free crystals was carried out. This paper reports the results, as well as a measurement of the temperature dependence of self-diffusion in a uranium. EXPERIMENTAL The single crystals of a uranium used in this experiment are listed in Table I, together with other experimental details. '(Mosaic structured" here means crystals grown by solid-state phase change.3 The Laue spots from such crystals spread over about 6 deg of arc, which indicates that the density of dislocations is very large. "Perfect" crystals are ones grown by Fisher's grain-coarsening tehnique; the Laue spots from these are quite sharp,4 which shows that the dislocation density in these crystals is much lower. All of the crystals were made from high-purity uranium; a typical analysis is given in Ref. 1. The actual diffusion directions were within a few degrees of the nominal. The thin layer-sectioning method was used. The experimental techniques were similar to those described in Ref. 1, except the sectioning. Crystals Za, 2b, 2c, 4a, 4b, and 4c were sectioned on a lathe. Crystals 3a, 3b, and 3c were sectioned by grinding on glass plates, with 1 p diamond powder in butyl alcohol as the abrasive. The use of glass plates eliminated the crowning noted in Ref. 1, and the use of butyl alcohol as a lubricant simplified the chemical processing of the sections. Material from the sides of these three crystals was removed by spark machining before sectioning. The sectioning of crystals 4a and 4c was botched. A small cylinder of metal was extruded from the center of crystal 4a while turning off material from the side of the sample. Crystal 4c was misaligned by 2.1 x 10"3 cm because the dial gage jammed during the alignment. Notwithstanding these errors, useful data were still obtained from these crystals. The points

Jan 1, 1967