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By Joseph W. Mills

In 1956 the discovery of nickel on Jumbo Mountain, Snohomish County, Washington, focused attention on this part of the Cascade Range, far more renowned for its timber than for its mineral resources. Hand specimens assaying as high as 13 pct Ni encouraged Discovery Mines Inc. of Mount Vernon, Wash., to stake 12 claims in Township 31 North, Range 9 East of the Willamette Meridian. The property was leased to Climax Molybdenum Co. in January 1957. Trenching, sampling, and geologic studies were carried out during the late summer of 1957 when most of the snow had disappeared. Although the deposits are only about four miles south of the logging town of Darrington and about two miles, as the crow flies, southeast of the end of a good gravel road from that town, all camp supplies and equipment were air-dropped, owing to the extremely rugged nature of the terrain.

Jan 3, 1960

SAN FRANCISCO LOCAL SECTION Executive Committee G. HOWELL CLEVENGER, Chairman C. W. MERRILL, Pace-Chairman JAMES C. RAY, Secretary-Treasurer, 1235 Webster St., Palo Alto, Cal. F. W. BRADLEY ANDREW C. LAWSON Meets on the second Tuesday of each month Farewell Dinner to H. Foster Bain H. Foster Bain, Who has gone to London to assume the editorship of the Mining Magazine, was tendered a farewell dinner by the San Francisco Sections of the American Institute of Mining Engineers, the Mining and Metallurgical Society of America, and the Engineers' Club, on the evening of Mar. 9, 1915, at the Hotel Bellevue, San Francisco, 85 members being present. George H. Clevenger acted as Toastmaster and the following toasts were responded to: Bain and the Mining Industry, E. H. Benjamin. Bain, the Geologist, A. C. Lawson. Bain, the Man, F. W. Bradley. Bain, the Friend, C. W. Merrill. Bain, the Schoolboy, C.. F. Tolman. The Frontispiece and Flow sheet from the souvenir program, designed by James C. Ray, Secretary of the Section, are reproduced herewith.

Jan 5, 1915

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By James R. Gage

THE lead deposits of Missouri may be divided into three districts, the southwest, middle, and southeast. As too much time would be required to devote a detailed account to each district, only a description of the modes of occurrence of the lead ores in the southeast district will be given. The lead mining region proper of Southeast Missouri is embraced in an area of about twenty-five miles in width by about one hundred in length. The country embraced in this district is very broken, and traversed by ridges from one hundred to three hundred feet in height, with an occasional knob rising higher. Porphyry forms almost the entire substructure of the region, with here and there outcrops of granite. The crystalline rocks were eroded into ridges and valleys before the deposition of the limestone took place. These porphyries are older than the Silurian limestones, and "belong (according to Pumpelly) to the Archaean (Azoic) formation, of which they may be the youngest member in Missouri. They are the near equivalents, in point of age, to the great iron-bearing rocks of Lake Superior, New Jersey, and Sweden."12/02/2007

Jan 1, 1875

By J. A. Jaekel, W. C. Aitkenhead

Uranium deposits in the Spokane Indian Reservation, as well as those around Mt. Spokane, are essentially low grade, much of the ore containing less than 0.2 pct U3O8. The Mining Experiment Station of the Division of Industrial Research, State College of Washington, has been engaged in intensive research on the amenability of these low grade ores to froth flotation. The results: successful flotation of autinite, chief mineral constituent. At the outset of this work the goal was a concentrate of 1 pct U3O8 with a 90 pct recovery from ores containing less than 0.2 pct U3O8. Most of the work has been done on argillite ore from the Midnight mine on the Spokane Indian Reservation. The goal has not been attained using this ore, but samples of the granite ore from Mt. Spokane yielded successful results. For example, a concentrate containing 11.2 pcl U3O8 was produced from a Mt. Spokane high grade ore containing 1.27 pct U3O8 with a recovery of 97.8 pct. Another Mt. Spokane ore yielded a concentrate of 5.0 pct U3O8 from an ore containing 0.13 pct U3O8. with a recovery of 85 pct. This same ore gave a recovery of 93.5 pct when the grade of concentrate was reduced to 2.0 pct. It has been concluded that a successful method for floating autunite has been developed and that the mediocre results from the Midnight argillite ore are probably caused by the presence of some other uranium mineral or minerals less amenable to these reagents. The experimenters tested a third type of Washington ore, found on the Northwest Uranium Mines Inc. property on the Spokane Indian Reservation. This is a conglomerate of pebbles and small boulders of partially decomposed granite and is shot through with autunite. Its characteristics lie between those of the Midnight ore and the granite ore from the Spokane district. It responds better than the ore from Midnight but not as well as that from Mt. Spokane. As the fatty acids are the only type of collectors showing promise, investigation has been concerned with these acids and the optimum conditions for their use. The first method for treating the argillite ore from the Spokane Indian Reservation made use of Cyanamid's R-708 as a collector, a tall oil product described as a substitute for oleic acid. Although the investigators proved that R-708 is a collector for autunite when mixtures of autunite and silica sand are used, results on the ore were mediocre. Tests of other fatty acids revealed that the solid fatty acids of the saturated series are collectors for autunite and that their collecting power increases with the length of the carbon chain. The even carbon members of the whole series were tested from the 10 carbon acid (capric) to the 22 carbon acid (be-henic). The least expensive collector, stearic acid (18 carbon), proved to be a good one, so this was used in most of the tests. In first attempts with stearic acid, the collector was dissolved in various hydrocarbons and the solutions were added to the flotation cell. Cyclohexane, gasoline, fuel oil, kerosene, and other solvents were tried. Small amounts of high grade concentrates could be brought up, but recoveries were low. Finally emulsions of stearic acid were tried. It was discovered that stearic acid alone has little collecting power except when conditioning is carried out at high temperature. When hydrocarbon solvents were also present, it proved to be an excellent collector. An example of one emulsion that proved satisfactory for some ores is given as follows: 1 part stearic acid by weight, 1 part sodium oleate by weight, 1.2 parts kerosene by weight, 100 parts water. In some successful tests part of the stearic acid was replaced by oleic acid. The emulsions were made by agitating the stearic acid and sodium oleate together with hot water, then adding the kerosene and agitating while cooling. In the five tests reported in Table 1, 650 g of ore were ground with 650 cc water in a laboratory rod mill. The pulp was filtered to eliminate excess water and the ground ore transferred to a stainless steel beaker for conditioning at high pulp density. In most of the tests sodium hydroxide was added to the conditioner during agitation, then the collector emulsion, and finally the sodium silicate. The amount of alkali was adjusted to give a pH of 8.5 to 9.0 in the flotation cell. After conditioning the pulp was transferred to a laboratory flotation cell and the test completed in a normal manner. It is interesting to note that a deposit of high grade concentrate forms on the conditioning agitator and in the conditioning vessel, and at times on the agitator of the flotation cell itself. A few grams of concentrate running as high as 4 pct U3O8 were recovered from the conditioner when Midnight ore containing less than 0.2 pct U3O8 was treated. In the examples given in Table I this conditioner concentrate is calculated as part of the total concentrate. The authors have not yet fully explored the possi-

Jan 1, 1960

By W. G. Pfann

A simple method of obtaining multistage batch separations by crystallization was described recently. Known as zone-refining, it comprises passing short molten zones through a long solid charge. This technique can now be used on a continuous basis by means of the zone-void method described in this paper. Feed enters, at an intermediate point, a column down which molten zones travel, and waste and product leave at the ends. Materials move in the column through the agency of voids, which are introduced at the ends and travel toward the feed inlet. The voids and molten zones are moved by external heaters in a simple manner, and the principle of reflux is utilized. ANEW method of obtaining multistage separations by crystallization was described recently.' Named zone-refinina.,-, the method comwrises slowly passing a series of molten zones through a long solid charge. Solute becomes concentrated at one or the other end of the charge, depending on whether it raises or lowers the freezing point of the solvent. The separation increases with the number, P, of zone-passes, approaching a limit as P approaches infinity. Zone-refining has been highly effective in purifying germanium and other substances.2,3 and new applications are steadily increasing. Zone-refining is a batch method and as such it has certain limitations inherent in batch operation. If it could be made continuous, its scope and utility would be greatly broadened. This end has been achieved by the zone-void method described in this paper. In the zone-void method feed is introduced continuously at an intermediate point in a column down which molten zones travel, while impure waste and purified product leave at the ends. Both the flows of feed, waste and product, and also the travels of the zones, are actuated by external moving heaters in a simple manner; and the system utilizes the principle of reflux. The method provides, in the field of crystallization, the counterpart of the continuous fractiona-tion column in the field of distillation. The following will be discussed: apparatus and mode of operation, fundamental nature of the separation, design theory, and practical considerations. The method will be described in terms of a binary solute-solvent system in which the solute is an impurity to be removed and the solvent is the desired product. The distribution coefficient, k, defined as the ratio of solute concentration in the solid freezing out of a molten zone to that in the liquid in the zone, is assumed to be constant and less than one. The process is equally effective for k's greater than one and for ternary or higher order systems. Method and Apparatus The essential features of a continuous zone-refining process are represented in highly generalized form in Fig. 1. A series of molten zones, produced by moving heaters, travels slowly down the column or charge (to the left in Fig. 1). If there were no flows of feed, waste, or product, the process would simply be batch zone-refining, the action of the molten zones being to sweep solute down the column, solvent up the column. For the process to be con- tinuous, with stripping and enriching sections in the column, feed must enter, and waste and product must leave, as indicated. The zone-void process accomplishes both objectives, namely, the indicated movements of zones and the indicated flows of material. Zones are moved by moving heaters, just as in batch zone-refining. Materials are made to flow by creating voids at the waste and product exits and causing these voids to move to the feed inlet. Since there must be a net flow of material from the feed inlet to each of the outlets, the indicated movements of voids are in the desired directions, because movement of a void in a given direction corresponds to flow of material in an opposite direction. In order to produce the desired movements of voids, the column is folded into two vertical sections having the feed inlet in common at their upper ends. Voids are displaced upward by the liquids in the molten zones and their travel is actuated by the motions of the zones. Voids travel with the zones in the enriching section and move continuously. Voids travel opposite to the zones in the stripping section and move intermittently. Creation and travel of voids will now be examined in detail. The enriching section of a column in operation, with its void generator, is shown in Fig. 2. The column section is a vertical tube around which a series of closely fitting, regularly spaced heaters travel slowly upward. Each heater produces a molten region, the temperatures of the heaters and the cooling between heaters being controlled so as to maintain the molten zones approximately constant in size. A void is normally present atop the molten zone in each heater. As the heater rises, it continuously melts solid above it, which drips through the void into the molten zone and continuously freezes out solid below it, of concentration k times that of the liquid in the zone. When a molten zone and void reach the feed inlet, which is kept molten, the void is displaced by an equal volume of feed liquid. Generation of voids of controlled size in the enriching section is shown in Fig. 3. The void generator is a tube of small cross-section, provided with lateral heat-conducting fins which sense the position of the heater. Liquid can escape only when the entire outlet tube is within the heater. If any part of the outlet tube is outside the heater, liquid cannot escape,

Jan 1, 1956

By Kendall E. Born

Production of crude oil in Tennessee during 1941 was slightly more than 15,000 bbl., about the same as in the preceding year. Two thirds of the total was from the Mississippi limestone pools in Scott and Morgan Counties. About a dozen small scattered wells in Clay, Pickett, and Fentress Counties, pumped irregularly, produced approximately 5000 bbl. Natural gas was marketed from wells in Morgan and Fentress Counties for consumption in the Sunbright and Jamestown areas, respectively. The production by counties is shown in Table I. Drilling activities in the state fell to the lowest stage since 1933. Twenty-seven wells were spudded in during 1941, of which six were drilling or only temporarily suspended on Dec. 37, 1941. Of the 22 completions, four were gas wells of undetermined quantity, but are classed as commercial, and 17 were dry or near-dry holes. One well encountered oil, but it has not been tested. The total footage drilled during the year was 29,916 ft.; the average depth of wells was 1359 ft. The more important wildcats are listed in Table 2; the distribution of tests according to physiographic divisions is given in Table 3. East Tennessee.—One well was drilled to 3480 ft. in northwestern Anderson County, in the highly disturbed Appalachian area, a region long considered the most unfavorable in the state for the accumulation of oil and gas. Another test is now drilling below 2000 ft. in this general area. Cumberland Plateau.—There were two completions in the Cumberland Plateau area. One test, drilled in northwestern Scott County in an area of former Mississippi limestone production,' encountered a considerable amount of free oil at 850 ft., about the same horizon as in the old abandoned wells. No pumping tests have been made to date. A well at Oneida, Scott County, found gas at 1579 ft. in a sandy limestone of lower Mississippian age. The volume was reported doubled by a shot, although no open-flow measurement is available. Eastern Highland Rim.—Six completions on the eastern Highland Rim resulted in two small gas wells in Fentress County, which will be used to augment the supply for Jamestown. The producing horizons are shaly limestones of Ordovician (Trenton) age. Two wells in this area tested the upper part of the Knox dolomite group, one of which encountered some free oil in a sandy dolomite at 1670 to 1681 ft. A test high on a well-defined structure in Clay County found a considerable amount

Jan 1, 1942

By Kendall E. Born

Production of crude oil in Tennessee during 1941 was slightly more than 15,000 bbl., about the same as in the preceding year. Two thirds of the total was from the Mississippi limestone pools in Scott and Morgan Counties. About a dozen small scattered wells in Clay, Pickett, and Fentress Counties, pumped irregularly, produced approximately 5000 bbl. Natural gas was marketed from wells in Morgan and Fentress Counties for consumption in the Sunbright and Jamestown areas, respectively. The production by counties is shown in Table I. Drilling activities in the state fell to the lowest stage since 1933. Twenty-seven wells were spudded in during 1941, of which six were drilling or only temporarily suspended on Dec. 37, 1941. Of the 22 completions, four were gas wells of undetermined quantity, but are classed as commercial, and 17 were dry or near-dry holes. One well encountered oil, but it has not been tested. The total footage drilled during the year was 29,916 ft.; the average depth of wells was 1359 ft. The more important wildcats are listed in Table 2; the distribution of tests according to physiographic divisions is given in Table 3. East Tennessee.—One well was drilled to 3480 ft. in northwestern Anderson County, in the highly disturbed Appalachian area, a region long considered the most unfavorable in the state for the accumulation of oil and gas. Another test is now drilling below 2000 ft. in this general area. Cumberland Plateau.—There were two completions in the Cumberland Plateau area. One test, drilled in northwestern Scott County in an area of former Mississippi limestone production,' encountered a considerable amount of free oil at 850 ft., about the same horizon as in the old abandoned wells. No pumping tests have been made to date. A well at Oneida, Scott County, found gas at 1579 ft. in a sandy limestone of lower Mississippian age. The volume was reported doubled by a shot, although no open-flow measurement is available. Eastern Highland Rim.—Six completions on the eastern Highland Rim resulted in two small gas wells in Fentress County, which will be used to augment the supply for Jamestown. The producing horizons are shaly limestones of Ordovician (Trenton) age. Two wells in this area tested the upper part of the Knox dolomite group, one of which encountered some free oil in a sandy dolomite at 1670 to 1681 ft. A test high on a well-defined structure in Clay County found a considerable amount

Jan 1, 1942

By R. B. Woodworth

Discussion of the paper of R. B. Woodworth, presented at the New York meeting, February, 1916, and printed in Bulletin No. 107, November, 1915, pp. 2247 to 2312. R. B. WOODWORTH, Pittsburgh, Pa.-This is a very long paper. It is a structural engineer's contribution to the art of mining and is written from his standpoint rather than from that of the mining engineer, and is, therefore, a study in the development of drilling structures by one who has made it his business to design structures rather than mechanism and machinery and rather than to utilize those structures in the actual exploitation of oil and gas. Drilling practice varies widely in different oil and gas fields. The , problems of western Pennsylvania are much simpler than the problems of the Mid-Continent and of the Gulf Coastal Plain and these again are simpler than problems of the Pacific Coast. The history of the commercial development of oil and gas is recorded in the annual publications of the U. S. Geological Survey and other bodies whose business it is to make record of statistics. The mechanical and structural features of the art of drilling have not yet received adequate treatment by the historian. Scattered references may be found on the subject in almost any work dealing at large with petroleum and its production. These references, however, are to those particular aspects of the matter that were contemporary with the publications themselves, but so far as I am aware there is no continuous and comprehensive account written of the development of drilling structures from their beginnings down to the present time, and certainly the more modern application of steel in the construction of such structures has not previously had an adequate discussion. With this latter phase of the subject I have been intimately associated, indeed, taking to myself the credit for having, in a way, been responsible more than any one else in the United States for the application of steel in the manufacture of drilling structures, and the purpose of the paper which is now before you is to record particularly the steps in that development while the subject is still fresh and the data available.

Jan 5, 1916

By Karl L. Konnerth

THE rapidly increasing use of machinery for the mining of coal and operations incidental thereto has materially changed conditions from a safety standpoint. A few of the coal-producing states have recognized the need for specialized electrical equipment for use in mines and have introduced certain requirements in their State safety regulations, notably Pennsylvania. This paper discusses the principal problems involved in maintenance of such equipment. PERMISSIBLE: EQUIPMENT "Permissible" electrical equipment is equipment that has met certain prescribed standards for use in mines where hazardous conditions may occur and has been recommended by the U. S. Bureau of Mines. Such machinery is available on the market for most coal-mining operations--for instance, coal cutting, transportation, drilling, loading, working-place illumination, shot-firing and pumping. A notable exception is the trolley-reel gathering locomotive which, although its parts may be explosion-tested by the Bureau, has not been approved as permissible for the following reasons: I. The trailing cable is subjected to more severe service than on other equipment. 2. State regulations do not require that a working place be examined for methane before a locomotive enters it. 3. Even with two-conductor cable, imperfect or inadequate bonding may cause the emission of sparks at the wheels of the locomotive and at rail joints. 4. As the locomotive is equipped with a trolley pole, and as the trolley wire may be installed and used in unsafe territory in spite of rigid State regulations, a trolley-reel gathering locomotive is always a potential hazard. MAINTENANCE The proper procedure for maintenance of permissible equipment may be divided into three parts: (I) inspection, (2) actual maintenance and (3) changes or improvements to existing machines. To secure the fullest benefits through the use of permissible equipment it is necessary that all men involved understand the principles underlying the safety features of this equipment and realize the significance of defects, so that neglect and indifference in the maintenance thereof may be eliminated. Inspection From the standpoint of safety it is desirable no doubt to make a suitable inspection of permissible electrical equipment once a week, but the opening of every enclosed compartment at each inspection may do more harm than good. The openings to such compartments are closed with various types of covers very accurately machined, often made of the softer alloys to reduce weight, and fastened with a multitude of bolts, screws, washers, and other small parts. Frequent handling of these covers may cause sufficient damage to defeat their original purpose and intent.

Jan 1, 1941

By Paul F. Kerr

QUARTZ of a certain kind, is one of our strategic minerals, and Brazil is probably the one important available source. Crystals of quartz of suitable size and perfection for piezoelectrical application are rare; their most outstanding use is in radio work. Clear quartz, or "crystal," free from twinning, cracks, foreign particles of other disturbing lines of growth, and gaseous or liquid inclusions, is cut into plates which provide excellent control of frequency in broadcasting. The squares or rectangles are less than a millimeter in thickness and ordinarily on the order of 1 in. along each side. They are cut at definite angles with respect to the axes of the crystal, and ground with opposite surfaces parallel. Each small slab must be a section of one crystal, uniform throughout in atomic alignment. The thickness of the chip controls the frequency of a broadcast and it is most important to have the plates oriented and ground with utmost precision. Opposite surfaces are parallel to within 0.001 mm. and expansion or contraction due to the temperature is limited to one part in a million.

Jan 1, 1942

By R. E. Ogilvie, N. L. Peterson

Diffi-lsion measurements were conducted at all compositims in the bcc solid solution of the U-Nb system employing incremental couples at composition intemals of 10 at. pct. Diffusion coefficients were determined by the Matano method from concentration gradients obtained with the electron-probe microanalyzer. The activation energy for inter-diffi-lsion as a function of compositim shows three distinct regions: 1) 80 to 100 pct U.6= 30 kcal per mole; 2) 20 to 80 pct U, $ - 70 kcal per mole; 3) Oto 20 pet U, Q = i40 kcal per mole. The frequency factor, fi0 and the activation energy $ were found to be roughly related by the following equation: log Do ^9.7 X IO-5Q -6,6. The Kirkendall marker movement indicates that DU is larger than DNb between 16 and 100 pct U and DNb is larger than DU from 0 to 4 pct U. FOR practical as well as fundamental reasons, the rates of diffusion in alloys are of considerable consequence. Most solid-state reactions are largely dependent upon the diffusion of atoms through the lattice structure and along grain boundaries. The high-temperature strength and reasonable nuclear properties of niobium have prompted its use as a reactor material in contact with uranium fuel. Hence, diffusion data for the U-Nb system are of considerable importance. In the previous diffusion study1 on the U-Nb system using pure element couples, reliable data were obtained only in the range of 0 to 10 at. pct Nb due to the large variance of the diffusion coefficient with composition. Also, a large Kirkendall effect and considerable porosity in the uranium-rich areas of the specimen were reported, which suggests that the true diffusion coefficients are somewhat larger. The purpose of the present study was to obtain reliable diffusion coefficients at all compositions using incremental diffusion couples with intervals of 10 at. pct. In view of the abnormal self-diffusion be- havior of y uranium2-4 and some other bcc transition elements,&apos;-&apos; it was felt that a comparison of the interdiffusion coefficients in the bcc U-Nb system with those of Reynolds et al.9 for the fcc gold-nickel system might shed some light on the diffusion mechanism involved. Both systems have similar phase diagrams, in that complete solid solubility exists above a miscibility gap. EXPERIMENTAL PROCEDURE The uranium used in this investigation was obtained through the courtesy of Argonne National Laboratory. An analysis of this material detected only Si-30, A1-7, C-6, N < 10 and 0-18 ppm. The niobium was electron-beam melted material obtained from Stauffer-Temescal. The gaseous impurities were less than 50 ppm, and the spec troc hemical analysis showed Ta-500 and W-200 ppm. U-Nb alloys were prepared at composition intervals of 10 at. pct by melting the appropriate amounts of the pure elements in an arc furnace. The buttons were inverted and remelted 6 times to assure complete mixing. The buttons were then wrapped in molybdenum foil, canned in Zircaloy-2 or stainless steel, and hot rolled 30 pct reduction in thickness at temperatures between 850" and 1100°C. Alloys with 10, 20, 30, 40, and 90 at. pct Nb rolled quite easily under these conditions, but the 50, 60, 70, and 80 pct alloys remained brittle. After melting and rolling (when possible), the alloys were annealed for 24 hr at a temperature within 100°C of their melting point in a dynamic vacuum of better than 4 x 10-8 mm Hg. These treatments produced alloys which were homogeneous on a 1 p scale within the detectability limits of the electron probe. During fabrication, the alloys picked up as much as 100 ppm Mo and 100 ppm Zr. Other elements checked for but not found were Co, Cr, Fe, Mn, Ni, and Ti. The grain size of the annealed samples ranged from 3 mm for the uranium-rich alloys to 0.3 mm for the niobium-rich alloys. This permitted measurements of the concentration gradients in the diffusion samples without crossing more than one or two grains, thereby eliminating any grain boundary effects. The specimens were bonded by theU&apos;picture frame" technique as reported by Kittel.10 Specimens of composition b)U + (100 - x)Nb were sandwiched between two specimens of composition (x + 10)U + (90 - x)Nb after they were ground flat and parallel

Jan 1, 1963

By K. J. Gill, P. Chiotti, J. T. Mason

Thermal, metallographic, and vapor pressure data were obtained to establish the pkase boundaries and the standard free energy, enthalpy, and entropy of formation for the compounds in the Y-Zn system. Three coinpounds with stoichiometric formulas of YZn, YZn2, and Y2Zn17 melt congruently at 1105", 1080°, and 890°C, respectively. Four compounds with stoiclziometric formulas of YZn3, YZn4, YZn5, and YZn,, undergo perztectic reactions at 905", 895", 870º, and 685ºC, respectively. Three eutec-tics exisl in this system with the .following eutectic temperatures and zinc contents in wtpct: 875ºC, 23.2 Zn; 1015ºC, 51 Zn; 865ºC, 82 Zn. The YZn, pkase undergoes an allotropic transformation. In the two phase YZn2 -YZn alloys the trans.formation gives a weak thermal arrest at 750°C, whereas in the two phase YZn2-YZn3 alloys no thermal arrest is observed and the transformation occurs over a temperature range below 750°C. At 500°C the free mzergies of formation per lnole vavy from —18,090 for YZn to —53,430 fov YZr11 and corresponding enthalpies vary from -24,050 to -92,080. The free energies and enthalpies per g atom as a function of composition show a maximum for the YZn2 phase; the 500°C values are -9580 and -13,180, vespectively. 1 HE only information found in the literature on Y-Zn alloys was the observation reported by Carlson, Schmidt. and speddingl that Y-20 wt pct Zn forms a low melting alloy. The alloy was produced by the bomb-reduction of YF3 and ZnF2 with calcium in an investigation of methods for producing yttrium metal. The solubility of yttrium in zinc has been determined by P. F. woerner2 and reported by Chiotti, Woerner, and Parry.3 In the temperature range 495" to 685°C the solubility may be represented by the relation In these equations N represents atom fraction of yttrium and T is the temperature in degrees Kelvin. The purpose of the present investigation was to establish the phase diagram for the Y-Zn system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory yttrium sponge. Arc-melted yttrium buttons contained the following impurities in parts per million: C-129, N-12, 0-307, Fe-209, Ni-126, Mg-13, Ca < 10, F-105, and Ti < 50. Some of the alloys containing 70 wt pct or more of Zn were prepared from yttrium containing 5000 ppm Ti as a major impurity. Tantalum containers were found to be suitable for all alloys studied and were used throughout the investigation. The pure metals, total weight about 30 g, were sealed in 1 in. diam tantalum crucibles by welding on preformed tantalum covers. A 1/8 in. diam tantalum tube was welded in the base of each crucible for use as a thermocouple well. Welding was done with a heli-arc in a glove box which was initially evacuated and filled with argon. The sealed crucibles were enclosed in stainless steel jackets and heated in an oscillating furnace at temperatures up to 1150°C. Homogeneous liquid alloys were obtained within a half hr at these temperatures except for alloys containing less than 20 pct zinc. The latter alloys were held at 1000º to 1100°C for 2 to 3 days in order to obtain equilibrium. After the initial equilibrations the tantalum crucibles containing the alloys were removed from the steel containers and used directly for differential thermal analyses. Further annealing heat treatments for alloys in which peritectic reactions were involved were carried out in the thermal analyses furnace. After thermal analyses the tantalum crucibles were opened and the alloys sectioned and polished for metallographic examination. In the following discussion alloys referred to as "quenched" were obtained by quenching the sealed stainless steel jacket containing the tantalum crucible and alloy in water. The differential thermal analyses apparatus used was a modified version of the one described in an earlier paper., The graphite crucible was replaced by an inconel crucible, the nickel standard and sampie container were separated by a 1/8 in. MgO plate, no getter was used, and provisions were made to

Jan 1, 1963

By C. Laird, C. E. Feltner

May different kinds of dislocation structures have been observed in strain-cycled metals and alloys. In order to understand their pattern and causes, an experimental program has been carried out to determine the influence on the dislocation structures of the three variables: 1) slip character of the material, 2) test temperature, and 3) strain amplitude. The results show that at high strain amplitudes cell structures me formed when the slip character is wavy, and that these are progressively replaced by uniform distributions of dislocations as the stacking fault energy is decreased. At lower strains, dislocation debris is formed which consists primarily of dipoles in wavy slip mode materials and multipoles in planar slip mode materials. Temperature merely acts to change the scale of the structure, smaller cells, and clumps of dislocation debris being associated with lower temperatures. It is shown that the results for many metals fit this pattern, which Parallels that occurring in unidirectional deformation. DISLOCATION structures produced by cyclic strain (fatigue) have been examined in a number of metals by transmission electron microscopy. These studies have produced a variety of interesting and often seemingly conflicting results. For example, different investigators have reported such structural features as cells.le4 bands of tangled dislocations,4&apos;5 dense patches or clusters of prismatic dislocation loops, planar arrays,4&apos;10 and various combinations or mixtures of these different structures. Most of these observations have been made on materials which were initially annealed and cyclically strained at low amplitudes resulting in long lives. Recently we have reported observations of the dislocation structures produced in copper and Cu-7.5 pct Al cycled at large amplitudes, resulting in lives of less than 104 cycles.4 These results, examined in combination with those in the literature, have suggested that a common or consistent structural pattern exists. Variations in this pattern appear to be determined chiefly by the three variables, namely, the slip character of the material,4,11 test temperature. and the strain amplitude. To verify this interpretation, we have studied [he influence of the above three variables (in different combinations) on the resultant structures in cyclically strained metals. Copper, fatigued at room temperature, was chosen as a reference state to which all other observations can be compared. The effect of slip character has been investigated by employing fcc metals of different stacking fault energy. Thus aluminum which has a more wavy slip character than copper, and Cu-2.5 pct A1 having a more planar slip char- acter, have been examined. The aluminum samples were fatigued at 210°K thus making their homologous temperature equal to that of copper at room temperature. The influence of temperature has been evaluated by examining the structures in copper at room temperature and 78°K. Finally the effect of strain amplitude was studied by looking at the structures at amplitudes giving lives ranging from 104 to 107 cycles. All of the specimens were examined at the 50 pct life level at which stage the structures have reached a stable configuration.12 I) EXPERIMENTAL PROCEDURE Strip specimens, 0.006 in. in thickness, were prepared from base elements of 99.99 pct purity or greater. Specimens were fatigued by cementing the strips to a lucite substrate which was subjected to reverse plane bending. This method of testing has been described e1sewhere.7 After fatiguing, specimens were thinned and examined in a Philips EM 200 which was equipped with a goniometer stage capable of ±30-deg tilt and 330-deg rotation of the specimen. On the basis of separate calibrations,13 allowances were made for the relative rotation and inversions between the bright-field images and the diffraction patterns. II) RESULTS AND DISCUSSION The life behavior of the materials under different test conditions is shown in Fig. 1 in the form of plots of total strain range vs cycles to failure. Comparisons of structures produced in the different materials were made at amplitudes which produced equal numbers of cycles to failure. The influence of strain amplitude on the structures produced in the reference state material (copper tested at room temperature) is shown in Fig. 2. At the 104 life level the structure produced comprises cells similar to those previously observed.3,4 They are approximately 0.5 p in diam and the cell walls are generally more regular or sharper than those produced by unidirectional deformation.14 At the 10&apos; life level the

Jan 1, 1969

By C. W. Beattie, R. L. Solter

ALUMINUM-KILLED, low carbon steel sheets are used extensively for severe deep drawing and other difficult forming operations. They usually, but not always, have a characteristic grain structure in which the grains are elongated both in the lengthwise and in the transverse direction. As described by Burns and McCabe,&apos; a typical grain in the plane of the sheet has its two axes in that plane from 1 Y2 to 4 times as long as the axis normal to the plane of the sheet. Rickett, Kalin, and MacKenzieZ have also reported on the recrystallization behavior of such steel. The contrast in grain structures of fully processed sheets of aluminum-killed and rimmed steel is illustrated by Figs. 1 and 2. The elongated grain structure of the aluminum-killed sheet is not developed on all heats or lots of this metal, and studies of the factors controlling and influencing its formation are reported in this paper. Jeffries and Archerb tate that unstrained grains are normally equiaxed, but exceptions are common. For example, if a metal containing a material mechanically obstructing grain growth is subjected to considerable working followed by thorough annealing, it may exhibit grains consistently elongated in the direction of working. Our experiments demonstrate that aluminum-killed, low carbon steel is such a metal, and that the substance mechanically obstructing grain growth is aluminum nitride. The effectiveness of aluminum nitride in inhibiting grain growth has been found to be influenced by the degree of cold reduction, the rate of heating in annealing, the thermal history of the sample before cold reduction, and the residual aluminum content. A correlation between grain shape and austenitic grain coarsening temperature also was indicated and additional experiments demonstrated that aluminum nitride is also the principal cause for the fine grain characteristic of aluminum-killed steels. Manufacture In conventional practice, aluminum-killed sheet steel is manufactured from a low carbon steel containing approximately 0.02 to 0.07 pct residual (HC1 soluble) Al. With the exception of certain samples containing greater or lesser amounts of aluminum, the steels used in these investigations were within the following composition range: C, 0.03 to 0.06 pct; Mn, 0.28 to 0.38; S, 0.017 to 0.032; Al, 0.03 to 0.06; P, <0.01; and Si, <0.01. Properly heated ingots are rolled to slabs about 4 in. thick. After surface conditioning, the slabs are reheated to about 2300°F and hot rolled continuouslv to strip about 1/10 in. thick. The strip rolling is completed at a temperature of 1550°F or higher, and the strip is coiled, usually at a temperature near the lower critical transformation. After cooling, the strip is pickled to remove oxide, cold reduced 40 to 70 pet to final thickness, then annealed to 1250° to 1350°F in 20 to 80 ton charges, the size of which results in slow heating and cooling rates. Effect of Cold Reduction According to Sachs and Van Horn,&apos; the deformations of the individual grains in rolling are similar to those of the total volume. Thus individual grains would elongate in rolling according to the amount of cold reduction imposed. This is true theoretically, but as cold reduction increases the individual grains tend to fragment, and measured grain elongations become less than theoretical. The amount of grain elongation may be described by a numerical rating based on grain counts made by the intercept method. Specimens are polished normal to the plane of the sheet, with the polished surface extending parallel to the rolling direction. After etching, grain intercepts are counted along a 50 mm line on a micrograph of suitable magnification. In random locations parallel to the plane of the sample 20 counts are made and 20 are made in the thickness direction of the sample the average count in the thickness direction divided by the average count parallel to the plane of the sample gives a numerical rating of the grain shape called grain elongation. For example, a grain elongation of 2.00 means that the average grain is twice as long as it is thick. The average of both counts may be converted to grains per sq mm by a nomograph relating intercept counts and grain count. By the same procedure the grain elongation in the plane of the sheet but transverse to the rolling direction may be determined, using transverse metallographic samples. A comparison of theoretical and measured grain elongation was obtained on an aluminum-killed

Jan 1, 1952

By D. R. Irving

Prior to this time, ample supplies of high grade mineral fillers, such as clay, have been available close to consuming centers. Now depletion of these accessible deposits, coupled with other factors such as increasing demand due to population expansion and standard of living rise, has made development of upgrading techniques attractive to producers. Various investigations being carried out by the U.S. Bureau of Mines are described. Factors making the development of improved methods for upgrading clays attractive to producers include: depletion of accessible deposits of high-grade clays, rising transportation and labor costs, more exacting specifications, and increased demand resulting from an expanding population and a constantly rising standard of living. Industry recognizes the need for upgrading presently unusable materials and has cooperated with the U.S. Bureau of Mines by providing samples from submarginal deposits and by evaluating the products that USBM upgrades. Following are some examples of recent clay beneficiation work by the Bureau. FIRE CLAY BENEFICIATION At the Rolla Metallurgical Center, Rolla, Mo., the Bureau is conducting research to develop technically and economically feasible mineral-dressing methods to remove quartz, pyrite, and other impurities from submarginal fire clays. The research has been spurred by the growing shortage of high-grade bur-ley, flint, and plastic clays in the Missouri fire-clay district resulting from increased consumption and the low rate of discovery of new deposits of adequate quality. There apparently is ample tonnage of submarginal flint and plastic clays to maintain the industry for many years if such material can be upgraded to commercial quality. Samples have been submitted to USBM by several major producers of refractories, including A. P. Green Fire Brick Co.; Harbison-Walker Refractories Co.; Mexico Refractories Div., Kaiser Aluminum and Chemical Corp.; and Wellsville Fire Brick Co. Research on some samples has been completed and still is in progress on others. The Bureau has found that specimens containing quartz or pyrite in grains coarser than the accompanying clay generally can be upgraded either with a gravity table or hydraulic cyclone. The improvement in quality is notable not only in chemical analysis but in an increase in pyrometric cone equivalent (PCE) of one or more cones. As an example, consider the results attained on a sandy flint—a fine-grained mixture of kaolin and halloysite with quartz and minor quantities of iron and manganese oxides. Chemical analysis was: 35.4 pct alumina (A12O3) and 47.8 pct silica (SiO2). The sample contained 9.2 pct free silica as quartz. The PCE was 33. The sample was crushed to -10-mesh, blunged with water, and then stage-ground to -48-mesh. The ground sample was tabled to yield a clay fraction containing 37.6 pct A12O3, and 45.3 pct SiO2 of which 2.4 pct was free silica. The PCE was 34. Recovery of alumina by this process was 73.6 pct. Concentration of the same clay in the hydraulic cyclone was even more effective in respect to quartz removal. The clay fraction analyzed 38.6 pct A12O3, 45.0 pct SiO2 of which 0.5 pct was free silica as quartz, and had a PCE of 34. Recovery of alumina was 71.9 pct. The hydraulic cyclone was also effective in reducing the pyrite content of a plastic clay which likewise was a mixture of kaolin and halloysite, plus some pyrite, quartz, and carbonaceous material. It analyzed 30.6 pct Al2O3, 52.3 pct SiO2, 2.3 pct Fe2O3, and 0.76 pct S. The sample was blunged and screened through 10-mesh to remove some coarse pyrite, then ground to -65-mesh and cycloned to remove most of the remainder. The final product recovered 81.8 pct of the alumina at a grade of 32.3 pct A12O3, 50.9 pct SiO2, 1.4 pct Fe2O3, and 0.1 pct S. The PCE was 32-1/2, compared with a PCE of 31-1/2 for the crude clay. The fine beneficiated clays, of course, must be pelletized and dried or fired to meet commercial acceptance. This operation has already been solved by industry. Little progress has been made on two remaining problems. One is that of fine-grained impurities, not separable by table or cyclone. Flotation is being investigated to solve this. Although fine pyrite is readily rejected, a satisfactory quartz-clay separation has not been attained. The second problem, a stubborn one, is that of alkali. Samples containing as much as 5 pct potas-

Jan 1, 1961

By E. T. Turkdogan, P. Grieveson

Experimental results are presented for the rate of solution of nitrogen in a iron in the temperature range 750° to 873°C and in 6 iron in the temperature range 1410° to 1470°C. It is shown that the rate controlling process is diffusion of nitrogen into the iron. The diffusiting of nitrogen in a and 6 iron is derived from the results, and the temperature dependence of the diffusivity is represented by the equation D = 7.8 x e- 18,900/RT sq cm per sec. The solubility of nitrogen in a and 6 iron, in equilibrium with 1 atm pressure of nitrogen, has been measured. Using these results and other available data, it is found that the variation of the logarithm of nitrogen solubility with the reciprocal of absolute temperature is nonlinear. In an Appendix, some results of Darken and Smith are presented for the rate of solution of nitrogen in iron using ammonia + hyidrogen mixtures. These data also support the view that diffudsion of nitrogen in iron is the rate-controlling process when ammonia + hydrogen mixtures are used. A considerable effort has been made to obtain data on the solubility1-5 and diffusivity of nitrogen in a iron6-l2 because an understanding of the effect of nitrogen on the properties of steel must be based on an accurate knowledge of the properties of nitrogen in pure iron. However, no information is available concerning the kinetics of solution of nitrogen in a and 6 iron. Recently the authors13 have investigated the rate-controlling mechanism operating in the kinetics of solution of nitrogen in y iron. This study was directed to determine the rate-controlling processes for similar reactions with a and 6 iron as well as to establish values for the solubility of nitrogen in equilibrium with nitrogen gas in a and a iron. EXPERIMENTAL The procedure used in experiments to determine the rate of solution in cylindrical iron rods was the same as that described in a previous communication.13 Ferrovac E grade iron used in all experiments contained the following impurities in weight percent: C, 0.005; Mn, 0.001; P, 0.002; S, 0.006; Si, 0.006; Ni, 0.025; Cr, 0.002; V, 0.004; W, 0.02; Mo, 0.01; Cu, 0.001; Co, 0.01; 0, 0.007. After cleaning the surface, the iron rods were treated in an atmosphere of purified hydrogen for 17 hr before the reacting gas was introduced for known experimental times. After quenching, the samples were sectioned radially and analyzed for nitrogen. In addition to experiments using rods, iron foils were used in the measurements of solution rates of nitrogen in a iron. The foils of two different thicknesses were prepared by cold rolling Ferrovac E grade iron cylindrical rod to 0.051 and 0.152 cm. Foil samples were used in a rectangular form 5 cm long and 1.25 cm wide. The specimens were thoroughly cleaned of surface oxide with fine emery cloth and degreased with carbon tetrachloride immediately before entry into the furnace. The experimental procedure was the same as that used in the study with rods. At the completion of an experiment, the foil samples of the nitrogenized iron were analyzed for nitrogen after discarding 0.3 cm from the perimeter of the specimen. Iron foils were nitrogenized and denitrogenized in the a and 6 range with a gas mixture of 95 pct N and 5 pct H for times varying from 5 min to 2 hr. Results obtained for the average composition of nitrogen in iron for these experiments are presented in Fig. 1. Prior to the denitrogenization experiments, the samples were saturated with nitrogen at 1000°C and 0.67 atm N, giving a uniform nitrogen concentration of 0.0204 pct. According to the known a-y phase boundary in the Fe-N system,14 this composition lies within the ferrite region at temperatures 750" to 850°C. Use of this initial nitrogen content insured that reaction occurred between the gas and a single solid phase, a iron. Examples of the results for the mean concentrations of nitrogen in cylindrical iron rods, 0.356 cm radius for both the a and 6 ranges are given in Fig. 2. Typical examples of the results obtained for the radial distributions of nitrogen in rods are presented in Fig. 3. It appears that the results for radial distributions can be extrapolated to constant surface compositions which agree with the equi-

Jan 1, 1964

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins&apos; and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer&apos; type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..&apos; and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young&apos;s modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen&apos;s5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

By H. C. Gatos, A. D. Kurtz

WITH the growing interest in the mechanism of self-diffusion of metals, the study of accurate and convenient methods for determining self-diffu-sion coefficients appears highly desirable. It was with this objective in mind that the present investigation was undertaken. Gatos and Azzam1 employed an autoradiographic technique for measuring self-diffusion coefficients of gold. This method involved sectioning of the specimen through the diffusion zone and recording the radioactivity directly on a photographic film. Because of the very short range of the emitted ß rays in gold, the activity recorded on the film was essentially the true surface activity. With proper choice of the sectioning angle, sufficient resolution could be obtained and the entire concentration-distance curve recorded in one measurement. For the boundary conditions of the experiment, where an infinitesimally thin layer of radioactive material diffuses in positive and negative directions into the end faces of a rod of infinite length, the solution of the diffusion equation is C/Cn = 1/v4pDt exp (-x2/4Dt) where C is the concentration of diffusing element (photographic density in this case), C,, is the constant (depending upon amount of radioactive material), x is the diffusion distance, D is the diffusion coefficient, and t is the time. Thus, by plotting the logarithm of the concentration vs the square of the diffusion distance, a straight line results and the slope contains the diffusion coefficient. In this manner, the self-diffusion coefficient of gold can be obtained as a function of temperature. In the present investigation the results reported by Gatos and Azzam1 have been verified, and the autoradiographic technique has been further developed and applied for the determination of the self-diffusion coefficient of gold at a number of temperatures. Furthermore, the energy of activation for the self-diffusion of gold has been conveniently determined. . Experimental Techniques Preparation of Specimens: The inert gold of high purity was received in the form of a rod from which cylinders were cut and machined to a diameter of 0.500 in. The specimens were annealed to a suitably large grain size and the faces were surface ground prior to the deposition of the radioactive layer. The radioactive isotope Au198 was chosen. It was produced in the Brookhaven pile by means of the reaction Au197 + n ? Au108. It decays by ß emission (0.96 mev) to Hg108 with the subsequent emission of a y ray (0.41 mev). 70Au 108 ? 80Hg 108 + -1e°. The half life of the Au108 is 2.7 days so that a strict time schedule had to be maintained in order to secure sufficient activity until the end of the experiments. For this reason, initial activities as high as 10,000 millicuries per gram were used. The gold arrived in the form of foil and was evaporated onto one face of each gold specimen cylinder to a thickness of about 100A. A sandwich-type specimen was formed by welding two such cylinders together. Evaporation of Gold: The gold was evaporated under vacuum from heated tantalum strips which were bent in such a way as to limit the solid angle through which the gold was allowed to vaporize, thus insuring a more efficient utilization of the gold. The specimens rested on flat brass rings which had an inner diameter of 0.475 in. The entire specimen-holding assembly could be manipulated from outside the vacuum system by means of a magnet which attracted a slug of soft iron attached to the assembly. By evaporating inert gold on glass slides under conditions identical to those employed for the radioactive gold, it was found that the thickness of the films was about 100A. Welding: The welding was performed by hot pressing in a stainless steel cylinder. The inside of the cylinder was threaded and fitted for two plugs. The specimens to be welded were placed in the middle of the cylinder and two pressing disks, one at each end, were inserted to avoid shearing stresses as the plugs were tightened. Mica disks were placed between the pressing disks and the specimens to prevent them from welding. The plugs were then tightened with a hand wrench and the entire unit was placed in an argon stream for about an hour to remove the oxygen. The unit was then inserted in the center of an argon atmosphere furnace maintained at about 700°C and left there for about an hour. Because of the difference in the temperature coefficient of expansion of the two metals, as the temperature rose. the pressure on the specimen-rollple increased and a weld resulted Welding was generally satisfactory under the conditions described.

Jan 1, 1955