Search Documents

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

No records have been found of coal in the old Spanish documents, although some mention of it probably exists in manuscripts. Coal was found in Mt. Diablo, in Contra Costa County, about five miles south of the San Joaquin River in 1852, but the first mine, the Teutonia, was located in 1858. The deposits are located on both sides of a high ridge, and vessels of 1,000 tons burden could ascend the river to the nearest point to the mines.1 In 1854, coal was found about four miles from Oroville, on the Feather River, in Butte County. Development work was started and in 1856 a mine was opened. From the description the coal was likely a variety of lignite and probably never amounted to anything commercially, as it does not appear again in the records 2 The more valuable mines at Mt. Diablo were opened in 1859 and 1860. By 1867 there had been 11 mines started and at that time five were in operation. The seam conditions were much disturbed and lack of knowledge of them caused much waste of effort and money. All of the coal excepting that used locally and in nearby towns, was shipped to San Francisco, and largely used for steam purposes. The first receipts were in 1861-6,620 tons. A railroad to the river had been constructed and opened in February 1866. The Corral Hollow field in Alameda County was found and prospected to a small extent in 1862. Two mines were opened but little work was done and the field was then abandoned. Good exposures were rare and the cost of underground exploration was then prohibitive. The Commercial mine produced coal in 1869 and 1870, but a fire in the latter year destroyed the tipple and communications to the mine. The Livermore mine was abandoned after 18 months operation in 1875 and 1876 and no other work was done here until the nineties. In 1867 Hyne reported the presence of coal in workable thickness, and of good quality, on the property of the Pacific Coast Petroleum Company,

Jan 1, 1942

By Charles E. Locke

PROSPERITY of the gold miner has continued with attendant construction of numerous plants, many of them small but some of good size. Many new mills have been erected in Canada and in the Philippines, end one should mention the new mill at Cripple Creek, Colo., a custom plant allowing a choice of flotation, cyaniding, or roasting and cyaniding. Flotation is a feature of many of the new plants and some existing mills have been remodeled to use flotation in place of amalgamation and cyaniding. The Utah Copper Co. has re- opened its Arthur mill and operations are being resumed in the big Ray, Chino, and Inspiration copper mills. Examples of new construction are the Mountain City 300-ton copper flotation mill in northern Elko County, Nevada; the Star zinc mill and one or two other mills in the Coeur d'Alene district of Idaho; and the 500-ton mill for the Buena Vista mine at Stewart, B. C. The last-named is to be installed underground, following the example of the zinc mill at Gilman, Colo., and he small Doyle jigging plant in the Wisconsin zinc fields.

Jan 1, 1937

By Enid C. Plante

To extend our knowledge of the flotation behavior of sulphide minerals, the response of the following minerals to ethyl xanthate as collector was studied by captive bubble and cylinder flotation tests: antimonite (Sb2S3), arsenopyrite (FeAsS), covellite (CuS), rnarcasite (FeS2), orpiment (As&.), pyrrhotite (FeS) and tetrahedrite (4CU2S, Sb2S3). Lollingite (FeAs2) was also exarnined to determine if its behavior could be correlated with that of pyrite or rnarcasite (FeS2. Experimental Method Mineral for Flolation and Contact Tests Mineral was prepared in the manner a1ready described1 and its behavior both freshly ground and "oxidized" was studied. Tests in which the mineral was allowed to oxidize for various periods showed that a uniform response to xanthate was reached in two days or less. Oxidation Products The soluble oxidation products from most of the above minerals were measured and their effect on the flotation of the mineral studied. The mineral samples were wet ground to minus-52 mesh and deslimed, and 20 g of this material placed in 200 ml of distilled water of a measured pH value, and CO2-free air bubbled through each suspension at a constant rate (about I bubble/sec) for 5 days. It has been shown1 that the size of the mineral is unimportant in the rate of formation , oxidation products and that probably the supply of oxygen to the mineral is the rate-determining step. At the end of 5 days the pH value of the 'supernatant liquid was measured again, the mineral filtered off and the soluble products determined. Methods for estimation of sulphur acids, ferrous and ferric iron and copper have already been described.l No satisfactory method was found for antimony. Arsenic was estimated as the arsenate.2 Flotation of "Unoxidized" Minerals with Ethyl Xanthate as Collector Fig I to 3, 4. 6, show the effect of alkali and cyanide as depressants for the minerals with 25 mg potassium ethyl xanthate per liter as collector at 35°C. Wark and Cox8 have shown that with ethyl xanthate as collector, galena, pyrite and chalcopyrite show a greater tolerance to cyanide and hydroxyl ions at room temperature than at 35°C Covellite (Fig I), marcasite (Fig 2) and pyrrhotite (Fig 3) behave similarly. The independence of the curves for pyrrhotite at 35°C with respect to cyanide

Jan 1, 1949

By M. Guney, A. R. Bell

In Mindola mine on the Zambian Copperbelt, there is a plan to extend the current production level of 1.2- 1.5 km (3,900-4,900 ft) with five additional production levels. Research work indicated that the present total heat output of 38.6 MW will inevitably increase to 63.2 MW in 25 years. Estimated WE and DB temperatures, representing the total heat generation in stope faces and development headings during these same periods are predicted to increase to 33.8/40.2°C (93/104°F) and 35.3/42.1°C (95/108°F) respectively. It is assessed that the nominal refrigeration capacity needs to be progressively increased to 9,000 M W.

Jan 1, 1984

By D. K. MACKAY

The production of oil and gas in Arkansas is confined to two distinct and widely separated regions of the state; namely: (1) South Arkansas in the Gulf coastal plain, where 49 fields-many containing two or more reservoirs or pools-yield oil, condensate and gas from beds in the Cretaceous and Jurassic, and (2) Northwest Arkansas, a part of the Arkansas Valley, where only dry gas is produced in 21 fields from sandstones of Pennsylvanian age. Exploration during the year 1945 centered largely in these two producing regions, but some of the geophysical surveys were made and wildcat drilling was done a considerable distance outside these regions.

Jan 1, 1946

By Carls Benedicks

It is well known by every one who has had to deal with boiler tubes that these are often seriously affected by a sort of corrosion, occurring as a local pitting, that frequently causes a perforation of the tube in a rather short time. The characteristic appearance of this corrosion is shown in Fig. 1. A very similar corrosion occurs in condenser tubes (Fig. 2).l A study of the microstructure or local chemical composition of the metal (iron 70:30 brass) fails to reveal any cause for this pitting. Of course one might possibly assume the starting point to be some oxide particle, causing an electrolytic local action, but this in no way explains the continued corrosion, progressing even when the assumed oxide particle must have disappeared. By the excellent work done by the Corrosion Research Committee of the Institute of Metals, and communicated, in October, 1923, to the Institution of Engineers and Shipbuilders in Newcastle-on-tyne, stress was laid on the faot that a content of entangled air has a very obnoxious effect. In the following correspondence, Sir George Goodwin stated that "engineers have, for a long time past, regarded air as the big enemy to be fought against in all questions of corrosion'72 and Kenneth Fraser pointed out that the most vital point is "the avoidance or removal of possibly the chief cause of present day corrosion, i. e. entrapped air and gases brought out of solution."3 In their reply, however, the authors state that they had "never for a moment believed that entangled air was responsible for the beginnings of corrosion, and express the opinion that the gradual liberation of air could not account for localized corro~ion."~ On consulting the many textbooks on corrosion, as that

Jan 1, 1925

By Harrison R. Cooper

This section will outline procedural, statistical, and model applications developed for specific problem solving and for specific applications in beneficiation processes. Iron Ore Processing Introduction of taconite as a basic raw material in the iron ore industry took place with application of high order technical resources for process development and engineering. This investment of resources encouraged computer utilization to maximize efficient use of capital. From this recognition, process control computers have been installed for operations use in the major taconite plants of the iron range. One of these installations, the Minntac Division of U. S. Steel at Mountain Iron, Minnesota, is described in the paper by Chase in these proceedings. Other computer techniques used in taconite processing are outlined by Tuttle, Ahlquist and Carlson, representing Erie Mining. In this volume Tuttle, et al. describe statistical methods for development of information in taconite beneficiation. Statistical methods used in iron ore processing are described by Volin in treating flotation data as outlined in prior proceedings of the symposia and in other publications. 1,2,3 Industrial Minerals The use of linear programming for feed blending at the Carlsbad operation of International Minerals and Chemicals was outlined by Nunnekoven in 1963.4 Subsequent application of this procedure at the Kingston phosphate operation in Florida was described by Loper. Continued development led to installation of an on-line computer in the Kingston plant which reached operational status in 1967.6,7,8 Application of an on-line computer to industrial mineral production accomplished at Kingston is regarded as a milestone in computer use development. Following this achievement, the Cominco potash beneficiation plant near Saskastoon in Canada was automated by installation of an on- line computer programmed to carry out direct digital control functions to effectively operate the plant by process computer. The procedures used in the Cominco operation are described by Madge in this volume. Development of a mathematical model

Jan 1, 1969

By R. F. Jones, N. E. Truitt, M. Prats

In most published discussions and theories of in situ combustion, the combustion fronts are assumed to be vertical. However, evidence from field tests leaves no doubt that combustion fronts often advance more rapidly along the top than near the bottom of a formation as a result of difference in density between injected air and formation liquids. The approximation proposed in this paper to determine the movement of the resultant tilted combustion surfaces states that the vertical rate of movement of combustion surfaces is proportional to the horizontal oxygen flux. Where self-ignition is possible, the proposed method demands that a secondary combustion surface exist around production wells which produce some oxygen. These secondary combustion surfaces may be formed long before the primary combustion surface can advance from injection to production wells. Heat liberated near production wells at these secondary combustion surfaces can contribute to an early increase in production rate. Results indicate that significant oil recoveries cannot be obtained from the usual flood patterns (five-spots, seven-spots, etc.) without producing large volumes of unused oxygen. Ideally, to increase oxygen- consumption efficiency, well patterns should allow oil production from a first line of production wells and gas production from more distant lines of producers. However, it may be desirable to produce some gas at all wells to support (and benefit from) active secondary combustion surfaces. Results indicate that the well spacing through which combustion can be advanced is larger than that predicted by other methods. A large number of production wells may still be desirable to take quick advantage of gravity drainage. From a comparison with results at South Belridge field, California, it appears that this method adequately describes oxygen concentration and temperature histories and combustion-front shapes. However, this method does not accurately locate the most advanced point of the combustion surface. There is some field evidence to substantiate the actual presence of secondary combustion surfaces at South Belridge. Use of the proposed method appears warranted at this time when lay-over of the combustion surface can be anticipated. INTRODUCTION The assumption of vertical combustion fronts has been embodied in all previous publicationsl-6 which use the movement of combustion fronts away from injection wells to determine the temperature and fluid distributions in the reservoir. The only paper concerned with a mathematical model of the combustion process in which a nonvertical combustion front is used was written by Gottfried.11 Actually, nonvertical combustion fronts have been observed in most in situ combustion field tests for which adequate data are available.7, 8, 6 In practice, the typical vertical extent of the burned zone decreases with distance from the injection well, and this burned zone is at or near the top of the sand body. In some cases, such as at South Belridge field near Taft, Calif., the combustion surface is almost horizontal over a very large area.8 Thus, for some years an obvious and serious gap has existed between theory (vertical fronts) and practice (tilted fronts). This is indicated in Fig. 1. Tilted combustion fronts such as observed at South Belridge8 sometimes result from the natural tendency of injected gases to rise to the top of an oil sand. An initially present gas cap, even if thin, would make apparent the effect of gravity segregation from the first, particularly since formations considered for in situ combustion field operations are generally selected for their

Jan 1, 1969

By G. F. Huff, G. R. Bailey, J. H. Richards

An improved bomb-sampling technique for obtaining samples for oxygen analysis from liquid steel is described. Analyses of samples taken from open-hearth furnaces by the improved method show sufficient agreement with laboratory data to indicate the accuracy of the method is better than that of other existing sampling methods. THE bomb-sampling method of determining the oxygen content of a liquid-steel bath was studied by obtaining and analyzing more than 200 samples from normal open-hearth heats. Of these samples, about 60 were obtained with a bomb of conventional design;' the remainder were taken with a somewhat modified bomb designed to give greater protection against slag contamination. In the new device, the contacting faces of the cast-iron mold halves are machined so that they fit closely; the opening at the top of the bomb is covered with a thin steel cap; and the top of the bomb is further covered with a wood block held in place by heavy steel wire. After the bomb has passed through the slag layer and has entered the steel bath, the wire melts and the wood block floats to the surface. Thereafter, the steel melts through the thin cap and flows into the bomb cavity where it is deoxidized with aluminum wire. An assembled bomb, ready for sampling, is shown in Fig. 1. To standardize sampling procedure, the samples were usually taken through the center door and at the bottom of the furnace; that is, the bomb was on the bottom when the metal cap melted. After each addition to the furnace, at least 20 min elapsed before a sample was taken. The oxygen contents of all the samples were determined by using the vacuum-fusion method, two or more specimens from each sample being analyzed. The specimens were cubes of metal cut from a region in the interior of the bomb sample, as shown in Fig. 2. Drillings for carbon analysis were obtained immediately above the oxygen-analysis region. Reproducibility of Results In determining the reproducibility of the results obtained with the modified bomb, the following four factors were studied: 1—variation in the oxygen concentration of duplicate specimens taken from a single sample; 2—variation in the oxygen concentration of duplicate samples taken in quick succession: 3—effect of the amount of aluminum wire

Jan 1, 1953

By E. N. Mazza, H. S. Kalish

The effect of sintering types 302, 3028, and 430 stainless steel powder compacts in hydrogen and dissociated ammonia was investigated. It was found that sintering in dissociated ammonia resulted in as much as 0.5 wt pct increase in the nitrogen content of stainless steel even though the dissociation of the gas was complete. Sintering in hydrogen, on the other hand, reduced the nitrogen content of the stainless steel to less than 0.01 wt pct. In the case of the 302-type stainless steel, the low nitrogen content resulted in a material that was largely ferritic, whereas the high nitrogen content rendered the material fully austenitic. Sintering in dissociated ammonia resulted in lower density, generally lower tensile strength, less ductility, and higher hardness than sintering under equivalent conditions in hydrogen. The reduction of oxides on both stainless steel and iron particles was found to be effected by hydrogen partial pressure in the sintering atmosphere. Compacting pressure was found also to effect oxide reduction during sintering. DISSOCIATED ammonia often is used as a substitute'.' for hydrogen in sintering and in annealing, since economic advantages sometimes can be obtained by such a substitution. In addition, anhydrous ammonia contains very little impurity. Thus, dissociated ammonia gas is very dry whereas tank hydrogen often must be freed of oxygen and water vapor prior to use in many applications. The sintering of stainless steel powder compacts as well as bright annealing is well recognized as requiring a hydrogen atmosphere and for the foregoing reasons dissociated ammonia is frequently substituted. It has generally been overlooked, however, that the nitrogen in dissociated ammonia might have an important effect on the sintering process and on the properties of stainless steel compacts. Considered an inert gas in many applications, nitrogen, on the other hand, is very reactive with cer- tain metals. Dissociated ammonia could not be used for hydriding zirconium or titanium. Nitrogen reacts with columbium, tantalum, chromium, uranium, thorium, and many other active metals. Iron and iron-base alloys are, for the most part, inert in nitrogen but there are many borderline cases. It has been reported that stainless steel stabilized with columbium or titanium should not be sintered in dissociated ammonia.3 olybdenum has been reported as reacting with dissociated ammonia to a minor extent.' Although most of the reactions with iron-base alloys are attributed to the action of un-dissociated ammonia and the action of nascent nitrogen, Uhlig4 showed how readily pure molecular nitrogen reacts with and diffuses into 18-8 stainless steel at 1150°C. He also pointed out how readily nitrogen diffuses out of 18-8 stainless steel when heated in pure dry hydrogen, and these thorough investigations on the subject show that commercial stainless steels are nitrogen-bearing, since they are melted in air. The effects of nitrogen in stainless steel, particularly the 18-8 Cr-Ni type, previously have received considerable attention." In 1926, it was pointed out

Jan 1, 1956

By S. Luszcz, R. W. Vook, Fred Witt

In situ X-ray investigations were made on polycrys-talline silver films deposited by vacuum evaporation on (111) CaF2 and (100) NaCl single-crystal substrates at 80°K. The films were evaporated and annealed in an X-ray diffractometer attachment having a residual gas pressure of 2 x lo-' Torr. All measurements were made without exposing the films to the atmosphere. Measurements were made on the films in the as-deposited state and after various annealing treatments. The intrinsic stacking and twin fault densities, the magnitudes of the uniform and nonuniform strains, and the crystallite sizes were determined. In addition the textures in the films were measured qualitatively. The results obtained for the as-deposited films on single-crystal substrates are in substantial agreement with previously reported results for silver films deposited on glass. Intrinsic stacking and twin faults, as well as uniform and nonuniform strains, were present in these films. During the various annealing treatments (up to 350°C) the faults and nonuniform strains annealed out. Considerable grain growth and texture changes occurred also. The effects were much greater for the NaCl substrate than for the CaFz substrate. The relative magnitudes of the grain growth in the variously oriented grains could be explained qualitatively in terms of the thermal strains and strain energies introduced into the differently oriented grains during the initial, irreversible anneal. These strains were due to the different thermal expansion coefficients of the film and substrate. X-RAY diffraction measurements on evaporated films deposited on substrates at low temperature have the advantage that many of the imperfections introduced into the film during deposition are "frozen in". Thus, the influence of a very important experimental variable, substrate temperature, on the imperfection structure of evaporated metal films may be studied. Moreover, the effects of annealing such films makes possible the study of thermally activated recovery processes in these films. The present study was designed to determine the influence of single-crystal substrates on the resultant film structure relative to the previous results obtained using glass substrates.' To this end great care was taken to keep the experimental variables the same in the two cases. Different experimental conditions would, of course, result in films having different physical properties. Again the initial substrate temperature was in the neighborhood of 80°K and the films were subsequently annealed to 350°C. The pure metal silver was chosen for evaporation, primarily because of its relatively low stacking fault energy and consequent high fault density in the as-deposited state. The silver films were formed by evaporation onto air-cleaved {ill} CaF, and (100) NaCl surfaces cooled to 80°K in an X-ray diffractometer attachment2 having a base residual gas pressure of 2 X l0-' Torr. The films were not exposed to the atmosphere until all of the X-ray data had been recorded. In this way one of the most important experimental variables, environment, could be well-controlled and reproduced. X-ray measurements were made at the temperature of deposition and included determinations of the diffraction line peak positions, line shapes, and integrated intensities. The peak position measurements were used to determine the intrinsic stacking fault densities and the average uniform strain in the film. The shapes of the diffraction lines provided information on the twin fault density, true crystallite size, and average nonuniform strain. The preferred orientation in the film was determined qualitatively from the integrated intensities. I) EXPERIMENTAL PROCEDURE The evaporator attachmentZ was charged with 99.999 pct Ag pellets positioned in a tantalum filament which had been outgassed previously at l0-8 Torr. The CaFz and NaCl single crystals were cleaved in air and then placed in position in the chamber so that their cleavage surfaces were on the diffractometer axis. The chamber was prepumped using a sorption pump, sealed off, and then baked at 150°C for 24 hr. The ion pump operated during the bakeout cycle. The substrate was then heated to 500° C by means of an auxiliary heater and kept hot until the rest of the chamber was cooled slowly to room temperature. This bakeout procedure consistently resulted in an ultimate pressure in the low lo-' Torr range. The substrate was then cooled down on 80°K. Its temperature was monitored by a thermocouple wedged into the rear of the copper substrate holder. The diffracted intensity and peak position of the 111, 222, and 333 CaF, lines were measured prior to evaporation. Nickel-filtered, pulse-height-discriminated copper radiation was used. Similar measurements were made for the 200 and 400 lines from NaC1. These measurements were used as a lattice parameter check and to determine the thickness of the evaporated silver films from the attenuation of the substrate lines. The evaporation rates were approximately 3A per sec for both films while the maximum pressures during evaporation were 3 x lo- ' and 7 x 10"8 Torr for the CaF, and NaCl cases, respectively. The film thickness was measured by the attenuation of the CaF, and NaCl substrate lines and by at optical interference method. Values of 1700 and 1500A, respectively, were obtained for the silver

Jan 1, 1969

By D. G. Westlake

NUMEROUS hydride habit planes in zirconium, Zircaloy-2, and Zircaloy-4 have been observed by various researchers and have been compiled by Louthan and Angerman.1 While only partial agreement exists on the identification of these habit planes, there is a growing consensus that a tensile stress applied on a polycrystalline rod during slow cooling will cause the hydride platelets to lie perpendicular to the tensile axis. walters2 agrees with Louthan and Angerman who reason that "The particular plane on which precipitation will occur is the plane that will result in the maximum relief of stress by precipitation of the low-density hydride." The experiment described below was initiated to test this hypothesis on a single crystal of zirconium. A single-crystalline tensile specimen of zone-refined zirconium, designated number 13 in a previous study,3 had a square cross section with one pair of parallel faces only 4 deg from the basal plane of the hcp structure. The tensile axis was about 86 deg from the (0001) pole, 14 deg from the (1010) pole, and 16 deg from the (1150) pole. The specimen was charged to 50 ppm H by allowing reaction with the correct amount of hydrogen at 1073°K, homogenizing at this temperature for 2 hr, and cooling in the furnace. Two- surface analysis revealed that hydride platelets had precipitated parallel to the three {1010} prism planes. The specimen was heated to 673°K, in air, for 16 hr to bring the hydrogen back into solid solution, and furnace-cooled to 573°K.* It was then stressed in ten- sion at 1.2 kg per sq mm. (This produced a resolved shear stress of 0.6 kg per sq mm for glide on the prism plane with the highest Schmid factor. A higher stress would have produced significant strain at this temperature because the critical resolved shear stress for prism-plane glide in this crystal was only 1.0 kg per sq mm at ambient temperature.) The poles of the three prism planes were at angles of 14, 46, and 74 deg to the tensile axis so that an applied stress would exert normal stresses on the three planes in the approximate ratios 10:5:1, respectively. As soon as the stress was applied, the sample was furnace-cooled to room temperature. It was ground on wet Sic paper and chemically polished in 50 parts HNO3, 50 parts water, and 7 parts HF before examination. The result of the experiment was negative; i.e., the three (1010) planes were of equal importance as hydride habit planes.* It must be admitted that the ex- periment is not entirely comparable to those performed by walters,2 Louthan,5 and Louthan and Marshall6 on polycrystalline materials. They have found that some critical stress (below the macroscopic yield stress) is required for stress-orienting the hydrides. The applied stress in the present experiment was, by necessity, smaller by an order of magnitude than the critical stresses they report for the various materials. If the critical stress was related to the microstructure, one might postulate that it should be decreased by increasing the degree of perfection of the metal lattice and by increasing the grain size. But the experiment above suggests that, for the extreme case of a zone-refined single crystal of zirconium, the critical stress lies above that which one can apply without introducing gross plastic strain as another variable.

Jan 1, 1967

By G. W. Traer

The distillation of bituminous coals at what is commonly termed low temperature, and the quantities, nature and adaptabilities of the products have been the subject of considerable experimentation, during recent years. Fortunately, the earlier work in this country was done by men whose scientific training qualified them properly to record and interpret the results of their experiments. The work of Prof. Parr, of the University of Illinois, is especially notable in this respect. Prof. Parr's work, added to that of English experimenters, demon-strated-certain things to a degree which is generally regarded as convincing. They have proved that a caking bituminous coal, when subjected to a temperature of not more than 1000" F. (preferably somewhat less) will yield light tar having low specific gravity (about 1.06) and high value; also, that this yield, with a given coal, will depend upon the percentage of hydrocarbons in the coal, the maximum temperature used, and the promptness with which the distillate gases are removed. It is assumed that air is excluded from the retort, and that the coal is subjected to heat for a sufficient time to drive off all of the tarry hydrocarbons. The results attained in the first, or low-temperature stage of the car-bocoal process, recently described by C. T. Malcolmson,1 corroborate these general principles. It is the purpose of the writer to describe other work of a practical nature, directed toward the commercial adaptation of these principles, which was begun nearly two years ago; this investigation was assisted by A. J. Sayers, of the Link-Belt Co., and Carl Scholz. The first step was to draft tentative designs for the handling of the coal and coke so as to produce a coke having a suitable structure for sizing, storage, shipment, and handling, without the necessity of briquetting. Prof. Parr's results had indicated that the rather open-pored volatile coke produced by him had a low ignition point, which would contribute toward easy control of the fire in stoves, house furnaces, fire-boxes, and boilers. It is recognized by those experienced in the marketing of fuels that the hard non-volatile coke from the high-temperature process,

Jan 1, 1920

By D. H. Polonis, M. B. Kasen

AN unusual thermal etching phenomenon has been observed on the surface of a Cu-Si alloy. The observations were made during studies of vacancy condensation pit formation which were reported in previous papers.1,2 Figs. 1 and 2 are photomicrographs of the surface of a Cu-4.8 pct Si alloy after heating in vacuo (3 x X mm Hg) to 525°C and subsequently holding at that temperature for 16 hr in an impure (air-contaminated) argon atmosphere. Under these conditions preferential removal of silicon from the matrix by oxidation results in a surface which is entirely a phase overlying an a plus y structure. The light areas of Fig. 1 are regions in which very little thermal etching has occurred, while the majority of the surface has experienced severe etching. Similar regions in Fig. 2 are seen as plateaus above contours produced by net transfer of material from the specimen surface. Twin boundaries are also visible in Fig. 2. The difference in matrix mi-crostructure between Figs. l and 2 reflects the par- ticular orientation of low-index planes with respect to the surface of observation. Thermal etching contours of this type have been studied in detail by Hondros and Moore Both of the photomicrographs show that one or more dark spots are located approximately at the center of every protected area; where two spots are in close proximity, the protected areas have merged. The microstructures indicate that the anomalous resistance to thermal etching is related to the presence of these spots. Williams and Hayfield have shown that local regions of unusually high oxidation resistance can be caused by a surface monolayer of atoms with a work function higher than that of the base material. The result is an inhibition of the rate of electron removal from the base material and a decrease in the oxidation rate. The source of the protected layer may be either surface diffusion from contaminants on the specimen surface or pipe diffusion of solute atoms followed by migration across the surface. In the latter case the driving force is a difference in chemical potential resulting in a Gibbs adsorption phenomenon. In the present case, chemical polishing of the specimen surface precluded contaminants of a strictly surface nature. Consequently, diffusion of impurity atoms from within the lattice appears to be the most tenable explanation of the observed phenomena. The authors propose that the structures of Figs. 1 and 2 reflect the diffusion of impurity atoms along extended dislocations within the individual a phase grains prior to surface oxidation. The central spots within the protected regions are seen as sites of dislocation emergence which have become locally decorated with oxide in the manner discussed in Ref. 1. Williams and Hayfield observed protected regions adjacent to the grain boundaries of iron-contaminated copper which they attributed to the segregation of iron to the grain boundaries coupled with high dif-fusivity along the complex dislocation array at such boundaries. No evidence of such grain boundary protection was observed in the Cu-Si alloy; this

Jan 1, 1964

By F. X. Tartaron

The comparison of actual energy of comminution with theoretical surface energy presents a wide gap. On the other hand, Solid State Theory presents a viewpoint that places actual energy of breakage in understandable relationship with the theoretical strength of materials. Therefore the physical background of comminution theory favors Kick's Law. A11 discussions of comminution theory appear farfetched when comparison is made of the actual energy of crushing with the energy input called for by thermodynamic theory. Quoting Taggart:' "The work required to crush halite was of the general order of 0.10 kg cm per sq cm of new surface produced (based on air percolation) whereas the theoretical energy of this new surface, based on thermodynamic calculation by a number of investigators is 1 x 10'4 kg cm per sq cm or the work expended was 1000 times the new surface energy — an indicated crushing efficiency of 0.10 pct." It is frustrating to probe into comminution theory with the prospect that the energy one is measuring is 99.9 pct waste energy. Do the laws of comminution deal with energy consumed by mineral breakage or with waste heat energy? There seems to be something wrong. Solid State Theory may provide the answer. The following statement is particularly apt to the situation: "The fundamental fact about metals and indeed all materials, is that they are much weaker than they should be. By this, we mean that if the stress required to cause a given plane of atoms to slip past a neighboring plane is calculated from basic atomic and Solid State Theory, the resulting number is some 1000 times too large to be accounted for by errors in approximations or assumptions. We know now that this is due to dislocations, and we even have a fair understanding of the details of the process by which dislocations make a crystal weak. An intriguing possibility which suggests itself, results from the discovery of very minute metallic crystals which are apparently free of dislocations and which have a strength approaching the ideal value for a perfect crystal." Here we have an extraordinary reversal of the situation. The actual energy for breakage is only one-thousandth the theoretical instead of 1000 times as given by Taggart. But the theoretical energy presented by Solid State Theory is the binding energy between atoms (or ions) in a crystal lattice. This is the kind of energy envisaged by Kick's law. The surface energy or the other hand corresponds to Rittinger's law. Comparison of theoretical with actual, on the basis of surface or on the basis of Rittinger's law, seems to present an absurdity; yet Rittinger's law is confirmed by an impressive array of experimental evidence. Comparison of theoretical and actual on the basis of Solid State Theory or, in other words, on the basis of Kick's law seems reasonable; yet there is not a scrap of evidence to verify Kick's law. The situation appears paradoxical, but the developments in the next section of this paper show that the paradox is a hint to a strange turn of events. ENERGY-WEIGHT FRACTION FUNCTION charles3 has presented a final equation showing the relation of energy consumed in comminution to size of product n{-1) a-n + 1 E is energy, C is proportionality constant, a and n are constants and k is the coarsest size in the ground product (size modulus). In the course of study of a large amount of experimental evidence, Charles discovered that in the general case, a-n + 1 approximated zero. For some reason, a and n differed only by unity. But if a—n + 1 = 0 within experimental error, then it is obvious that Eq. 1 states that it requires an infinite amount of energy to grind any sample to any size. This is a case where nature gives an absurd answer to a man-made mathematical equation, hence something is wrong with the equation. An adjustment must be made to fit the equation with experience. TO reveal the nature of the adjustment, the differential equation preceding the second integration in Charles' group of equations is given When Charles integrated the quantity xa-n it was almost impossible for him to realize that he was dealing with a special case of integration and that

Jan 1, 1962

By V. R. Garfias

Principal events in petroleum operations of Mexico during 1934 have been the completion of three producing wells in the Poza Rica area and the plans for the expansion of operations of the Cia. de Petroleos de Mexico, S.A. (Petromex). Production for 1934 is estimated at close to 38,000,000 bbl., an increase of 4,000,000 bbl. over the previous year; an increase due in large part to the successful development in Poza Rica. The output of the South fields (Golden Lane) and Tehuantepec fields also increased somewhat during the year. Production of natural gasoline increased from 382,000 to 431,000 bbl. in 1934. Crude run in local refineries is estimated at 26,000,000bbl., some4,000,000bbl. more than the previous year. Exclusive of bunker fuel exports totaled 24,000,000 bbl., or 3,000,000 more than in 1933. Domestic consumption increased approximately 500,000,bbl. during the year, reaching a total of close to 13,600,000 bbl., exclusive of ships' bunkers. A total of 148 wells were completed as compared to 91 in 1933 and 40 in 1932. In proven areas, 133 completions resulted in 54 producers and 79 failures. The 15 wildcats drilled during 1934 gave no encouraging results. Seven of these were located in the border zone of northeastern Mexico; three tested possible northeast extensions of the Northern fields; two were drilled for possible extensions of the "Golden Lane" and three were completed in the Isthmus of Tehuantepec. Fields Northern Fields (Heavy Oil District).—There were 34 producing wells and 71 failures completed in the Northern fields, as compared to 20 producers and 20 failures in 1933. Practically all new producers were drilled to the shallower San Felipe formation, while wells drilled to the deeper Tamasopo limestone encountered salt water. Production of the field totaled 11,890,000 bbl., a decrease of 7.5 per cent from the previous year. Acid treatment was attempted during the year in seven wells

Jan 1, 1935

By Edward J. Felten

THE oxidation resistance of chromium and Fe-Cr alloys is increased by small additions of yttrium or other rare earth metals.1,2 In addition, the presence of the additives increases the resistance of these alloys to spalling of the external oxide above 1000°C. This ability to prevent spalling appears to be related to the formation of an internal oxide in alloys containing yttrium or the other rare earth metals. The internal oxide is found in the form of a filamentary growth concentrated in the grain boundaries of the unoxidized metal. In alloys containing yttrium this internal oxide was found to be either Y2O3 Or YCrO3.' In an earlier report,' the growth of the external oxide was found to be controlled by diffusion through the oxide layer. Thermal balance studies were used to establish the kinetics of external oxide formation. In this related study the rate of growth of the internal filamentary oxide has also been studied. The results obtained indicate that the growth of the internal oxide is also diffusion controlled. Internal oxidation appears to occur in at least two ways. Using copper alloys containing small amounts of silicon, Rhines 3 found that between 600" and 1000oC a subscale was formed which consisted of particles of silica dispersed in the metallic matrix. The conditions requisite to internal oxidation as suggested by Rhines are: 1) a solubility of oxygen in the alloy, 2) the ability of oxygen to diffuse at an appreciable rate into the alloy, 3) the possibility of the formation by the alloying element of an oxide more stable than the oxide of the host metal, and 4) a relatively low solubility of this oxide in the metal. These conditions are fulfilled for a number of other copper alloys.3-5 Furthermore, the relationship between the depth to which the internal oxide is formed and the oxidation time follows the simple parabolic law.6 The activation energy for copper containing small amounts of silicon, germanium, iron, or manganese as calculated from Rhines data6 is about 48 kcal per mole. In some cases the internal oxide is found segregated at the grain boundaries, especially near the the surface. Observations of this type of oxide formation have been reported by stead,7 Rhines,* and Lustman. Evans" cites these cases as examples of the simultaneous movement of anions and cations during oxidation. Furthermore, Evans states that the presence of a minor constituent with a high

Jan 1, 1962

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.' When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.'4-'7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By A. R. Elsea, C. C. McBride

HIGH-TEMPERATURE alloys, that is, alloys that are strong at high temperatures, have become increasingly important with the development of modern aircraft engines. Many alloys of this type are available. However, metallurgists do not have a clear understanding of the phases or structures which are responsible for these high-temperature properties. If these basic factors were understood, it might be possible to make better or cheaper alloys for service at high temperatures. For this reason, an investigation of the fundamental factors promoting high-temperature strength in alloys was started at Battelle Memorial Institute. This was to have included a study of the relationship between the structure and properties of cobalt-chromium base alloys of the vitallium type. It soon became clear that the structure of vitallium is quite complex and that the equilibrium diagrams which should explain these structures were unreliable. As a result, the cobalt-chromium binary diagram was determined as the first phase of this investigation1. This diagram is shown in fig. 1. During the study of the cobalt-chromium binary system, it was learned that these alloys may pick up considerable nitrogen when melted and heat treated in air. The extent to which nitrogen affects the various reactions in cobalt-chromium base alloys was not known, but there were indications that this impurity might be responsible for some of the erratic test results obtained for vitallium. Consequently, nitrogen was the first ternary addition studied. Thereafter the work was extended to ternary additions of iron and of nickel. This paper describes the investigation of the effects of nitrogen, iron, and nickel upon the reactions in cobalt-chromium alloys with 80:20 and 68:32 cobalt-chromium ratios. Experimental Work Alloy Preparation: A series of cobalt-chromium base alloys containing various amounts of the third element being studied were made for both the 80:20 and the 68:32 cobalt-chromium ratios. Electrolytic chromium, cobalt, and iron, and reagent-grade nickel powder were used as melting stock. Table I contains the chemical analyses of these materials. The charges were melted in alun-dum thimble crucibles which absorbed chromium oxide and effectively deoxidized the melts. These crucibles were supported by close-fitting graphite sleeves so that if they cracked during melting the metal would not be lost. Carbon increases, during

Jan 1, 1951