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By D. Harker, E. Epremian

The constitution of the nickel-tungsten system has been studied by a number of investigators, the most recent of which are Ellinger and Sykes.1 On the basis of metallography, electrical resistivity and hardness measurements and some X ray diffraction work, they constructed a consitution diagram (Fig 1). Ellinger and Sykes report a0 for the alpha face-centered cubic phase (nickel saturated with tungsten) as 3.66?.‡ The gamma phase (tungsten saturated with nickel) is given as body-centered cubic, but no value of a. is recorded. At 43 pct tungsten by weight (approximately 20 at. pct) a beta phase is reported, but structure and lattice parameter are not known. Primarily on the basis of metallographic evidence, they conclude that beta is a new phase and rule out the possibility of formation of a superlattice since they- observe a new phase in the microstructure. Grube and Schlecht2 report an ordering reaction in a system similar to the Ni-W (Ni-Mo) and Harker3 has shown that NirMo forms a superlattice upon the pre-existing face-centered cubic lattice of the alpha phase. Elliniger arid Sykes observed a change in the diffraction pattern of a 4.3 pct W alloy upon aging and attributed it to the formation of a new phase. Thus, there appears to be some question as to the character of the beta phase reported by Ellinger and Sykes. The purpose of the present work is to determine precisely the structure and nature of the beta phase in the Ni-w system of X ray diffraction methods. Experimental Procedure One inch diameter ingots of 43.66 pct, 40.15 pct and 34.06 pct .tungsten by weight (19.8, 17.6 and 14.1 at. pct respectively) were melted and cast under vacuum from electrolytic nickel and pure wire filament grade tungsten. The ingots were soaked for 16 hr at 1300°C in a hydrogen atmosphere furnace, then swaged at this temperature and finally drawn to 0.020 in. diam wire. Some of the bar stock was retained in 1/2 in. diam rod for hardness and metallographic studies. Wire samples for diffraction work were sealed in evacuated quartz tubes and subjected to the various solution and aging heat treatments in a hydrogen furnace. X ray photograms were taken in a Debeye-Slierrer camera using copper K radiation filtered by nickel foil. Results X RAY DIFFRACTION The lattice parameters of the alpha and gamma phases at saturation were determined by an X ray photogram of the 19.8 at. pct W alloy after solution heat treatment at a temperature well within the alpha-gamma range above the peritectoid temperature (17 hr at 1150°C—oil quenched). The alpha phase was found to be face-centeted cubic with a. of 3.594 ± 0.001?, while the gamma phase was determined as body-centered cubic with a. of 3.158 ± 0.001?. Exactly the same phases and parameters were ohtained with the 17.6 at. pct W alloy for the same solution heat treatment. Thorough analysis was made of an X ray photogram of a 19.8 at. pct alloy sample in the quenched and aged condition (solution treated 1T hr at

Jan 1, 1950

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By M. E. Nicholson

IN order to understand how alloying elements influence hardenability through their effect on the rate of pearlite nucleation, it is advantageous to use a model to describe the mechanism of pearlite nucleation. The model which currently is most widely accepted has been described, among others, by Mehl et a1.1-3 and by Hultgren.4 Pearlite nucleation involves both the nucleation of ferrite and cementite.4,5 Cementite nucleates first, followed rapidly by the formation of ferrite at the cementite-austenite interface. The conclusion that cementite is the first phase to form during the process of pearlite nucleation is based, in part, on the observation that proeutectoid cementite is continuous with pearlitic cementite and that the orientation relationship between proeutectoid ferrite and austenite is not the same as that between pearlitic: ferrite and austenite.6,7 Recently, Smith" has suggested that the dissimilarity in orientation relations, instead of indicating the pearlite nucleation sequence, may be evidence that pearlite is nucleated in a grain adjacent to the one in which it is growing. Also, Modin9 as shown that ferrite in pearlite may be continuous with proeutectoid ferrite, and he has also shown that proeutectoid cementite is not always continuous with pearlitic cementite. Thus, it appears that the conclusion that cementite always initiates the pearlite nucleation process is open to serious question. The author believes that important evidence on the question of how pearlite is nucleated exists in the rates of pearlite nucleation of different steels. The following is a review and analysis of this evidence. If the nucleation of pearlite is considered as requiring the nucleation of both cementite and ferrite, then the time to nucleate pearlite consists of the time to nucleate the first phase to form, plus the time to nucleate the second phase at the advancing interface of the first. In the absence of a visible proeutectoid constituent, the second phase must be nucleated very soon after the first. If cementite is the first phase to form, the time to nucleate pearlite will be approximately equal to the time to nucleate cementite. Since the nucleation rate of a phase precipitating from solid solution increases with the degree of supersaturation, it would be expected that the rate of pearlite nucleation should increase with increasing carbon content. Digges10 has shown that the reverse is true. He determined the quenching velocity necessary to suppress pearlite formation in plain carbon steels as a function of carbon content. His results showed that pearlite formation could be suppressed with lower quenching velocities as the carbon content of the steel increased, at least up to 1.25 pct C, the highest carbon content he studied. Thus, it would appear that in plain carbon steels, in which pearlite is formed at the nose of the C-curve, the hypothesis that cementite nucleates first does not predict the observed change in nucleation rate. The validity of the current model of pearlite nucleation may be tested also by determining whether or not it predicts the relative influence of alloying elements on the nucleation of ferrite and pearlite. This can be done best by a consideration of the changes in a TTT diagram produced by a change in alloy content. Hultgren4 suggests that the general shape of a TTT diagram, as well as what constituents will form from austenite, can be predicted from the relative nucleation rates of ferrite and cementite. This is illustrated in the schematic diagram for a hypoeutectoid low alloy or plain carbon steel shown in Fig. 1. The C-curves for ferrite nucleation and for cementite nucleation are represented by AA' and CC', respectively, and the start of ferrite formation and pearlite formation are represented by AX and BC respectively. Adopting the current theory, Hultgren suggests that between X and C pearlite forms directly from austenite, since cementite nucleates more rapidly than ferrite in this temperature range. Conversely, at temperatures above Tx, ferrite is the first to nucleate and proeutectoid ferrite is formed. As proeutectoid ferrite grows, austenite becomes enriched in carbon, so that the cementite nucleation rate is increased. As a result, pearlite nucleation above temperature Tx is accelerated, beginning along BX and not along C'X. Temperature T, represents the temperature at which the nucleation rate of ferrite equals that of cementite. By extending this type of reasoning, using the principle that the nucleation rates of ferrite and cementite increase with increasing supersaturation of austenite with respect to these phases, it should be possible to predict the influence of carbon content on the shape of the isothermal transformation diagram. For a slightly higher carbon content than that of Fig. 1, the curve A A' representing the beginning of ferrite formation should be moved to the right, whereas the curve CC' representing the beginning of cementite formation should be moved to the left. For hypoeutectoid plain carbon and low alloy steels, this prediction does not agree with existing data. Instead, as the carbon content is increased, the pearlite curve moves to the right along with the ferrite curve and always appears to join it tangen-tially. This behavior is demonstrated by the TTT-curves of a series of manganese steels" shown in Fig. 2. In this figure, TTT-curves for four alloys containing 0.20, 0.40, 0.60, and 1.20 pct C are superimposed. The curves are identified in the figure legend. The letters F, P, and C are used to indicate the start of ferrite, pearlite, and cementite formation, respectively. In these steels, it appears that the nucleation of ferrite and of pearlite are related processes. As a result of the foregoing evidence, it is proposed that the formation of pearlite be considered as follows: Either ferrite or cementite may nucleate from austenite, then grow until the remaining phase is nucleated at the interface between the growing phase and austenite. (The growth of the first phase to form is assumed to be accompanied by a composition change in the adjoining austenite.) According to this model there are two modes of nucleating pearlite: 1—where cementite initiates the succession

Jan 1, 1955

By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature' not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953

Executive.. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS. ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, Jr., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L, YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman. JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALES. C. HUMPHREYS 4 BRADLEY STOUGHTON.

Jan 7, 1913

By H. Y. Hunsicker

A graphic method has been devised for three-di-mensional analysis of hot deformation and for correlating the amount and directionality of the deformation with resulting directional properties. Deformation is evaluated in terms of dimensional change ratios referred to three orthogonal axes. Since all combinations of the three ratios can be represented in a triangular coordinate field with logarithmic scales, a two-dimensional chart of extent of deformation and degree of asymetry is possible. The entire gamut of shape changes from upsetting through flat-rolling to rod-rolling is accommodated. The resulting coordinate system is a base upon which can be represented the properties of the wrought products measured in the directions of the axes employed fir evaluating the deformation. When property data are available for many types and amounts of deformation, a three-dimensional figure can be constructed, and the projection of this figure is referred to as a ''3d'' chart. Experience in using such charts to plan fabricating operations for a variety of thick-section forged and rolled products of heat-treated aluminum alloys has verified its practical value for optimizing directionality relationships. MechANICAL anisotropy of thick section products of heat-treatable aluminum alloys is recognized by producers and users of these products, and the extent of the directional differences is apparent in property tabulations included in handbooks, standards, and specifications.' Attention has also been directed to the existence of important directional differences in the resistance of these products to stress-corrosion cracking. Metallurgical structure factors responsible for these directional differences include, among other possibilities, shape and alignment of grains, voids and nonmetallic inclusions (when present), volume fraction and spatial distribution of secondary phase particles and solid-state precipitates, crystal-lographic textures, and Bauschinger effect. The contributions of the individual factors vary with alloy composition, heat-treated temper, type of working process (forging, rolling, extrusion), and the amount and directional nature of the deformation. In general, the cast ingot used as the starting material for producing these wrought products exhibits only a modest degree of directionality. A monotonic and continuous transition from this nearly isotropic state with progressive hot deformation would appear probable, assuming that the working temperature is sufficiently high to cause continuous dynamic recovery. Several years ago a project was undertaken to evaluate the effects of hot deformation and metallurgical structures on the directionality of thick wrought aluminum alloy products, and the method to be described was developed as an analytical tool in this investigation. DIRECTION NOMENCLATURE The nomenclature system adopted by industry for the three mutually perpendicular directions employed in testing aluminum alloy products includes four terms: "longitudinal", "transverse", "long transverse", and "short transverse". These terms are conventionally related to the external geometry of the product but also by implication to the deformation and resulting metallurgical structure. Occasions arise in which through use of unusual fabricating methods, intentional or otherwise, the structure does not have the usual relationship to external geometry or may be very complex because of inhomogeneity of deformation throughout the piece. The longitudinal direction is generally parallel to the primary rolling direction or to the direction of extrusion. In the case of forging, it is parallel to the direction of maximum extension (not maximum "working" or "flow", as frequently stated). The term transverse is applied to any direction perpendicular to the longitudinal direction in a product having symmetry about the longitudinal axis, and generally, although not always, the deformation to produce these forms is nearly symmetrical in the transverse plane. This term then may be applied to a round, square, hexagon, or other polygonal, symmetrical shape produced by extrusion or rolling or by forging, if produced by a simple, symmetrical drawing procedure. The type of microstructure generally associated

Jan 1, 1970

By J. L. Gregg

A STUDY of copper and silver base alloys was made with the object of finding, if possible, useful alloys subject to dispersion hardening. These studies led to the discovery of several alloys showing considerable dispersion hardening, the most important of which, the alloys of copper with iron, nickel, cobalt and chromium silicides, have since been very ably reported by M. G. Corson.1 This paper is offered as a few notes covering alloys other than those described by Corson and some further data on the silicide alloys.

Jan 1, 1929

HenRy Clay FRick, a pioneer in modern coke and steel industry and, in more recent years, one of the outstanding financiers of America, died on Dec. 2, 1919, at his home on Fifth Avenue, New York. Although he had been ill since election day, when he had an attack of indigestion which developed into ptomaine poisoning, his death was a surprise to all. He is survived by his widow, Adelaide Howard Childs Frick; a son, Childs Frick, one unmarried daughter, Helen C. Frick, and four grandchildren. A quiet funeral service was conducted at the Frick home on Wednesday afternoon by the Rev. Dr. Leighton Parks, pastor of St. Bartholomew's Episcopal Church. This was attended by members and very intimate friends of the family, Trustees of the Metropolitan Museum of Art, Officers of the Links Club, and Directors of the United States Steel Corpn. Henry Clay Frick was born Dec. 19, 1849, in West Overland, Westmoreland Co., Pa. His father, John W. Frick, was a farmer of Swiss ancestG, and his mother, Elizabeth Overholt Frick, a member of an old Mennonite family. Until he was sixteen, he spent his time at school, on his father's farm, and in his grandfather's distillery, where he kept books. He attended Otterbein University, in Ohio, for a year. Frick, learning that coke was an essential of the already rapidly developing steel business, early invested every cent he could get in coking-coal lands. With the help of an associate of his grandfather, he formed the corporation of Frick & Co., coke dealers, and acquired fifty-one ovens in the Connellsville region and 300 acres of soft-coal lands. During the panic of '73, with the help of Judge Thomas Mellon, a Pittsburgh 'banker, he bought out his partners and while coke was selling at 90 cents a ton enlarged his purchases of suitable lands. Later, the price of coke increased until it was selling at $5 a ton. Before he was 30 years old, Frick was rated a millionaire. Association with CaRnegie In 1878, he sold an interest in the business Do E. M. Ferguson of New York, and later a share to Mr. Ferguson's brother. Four years later the business was reorganized into the H. C. Frick Coke Co. with vast coal lands, great banks of ovens, and a capitalization of $2,000,000. Then began his association with Andrew Carnegie. He exchanged a part of his coke interest for shares in Carnegie Brothers of Pittsburgh,

Jan 1, 1920

By D. M. Collingwood

The year 1928 has been marked by scattered but considerable wildcat drilling considering the overproduction prevalent in the oil industry. This wildcatting has resulted in the discovery of oil in one interior salt dome, several small fields producing from serpentine, Taylor marl, and Austin chalk, and two new fields producing from the Edwards limestone, one of which in the Bruner or Salt Flat area of Caldwell County promises to be of major importance if not quite as large as the Luling field. Fig. 1 shows production by fields for 1928, compared in the case of the older fields, with that for 1927. New Production From Salt Domes Boggy Creek Dome This salt dome was discovered in 1927 by core drilling and deep tests recommended on the evidence of surface geology. A large block of acreage controlled by the Humble Oil & Refining Co. covers the dome. Since the discovery of the deep-lying salt plug and oil on the flank of this dome in 1927, development has proceeded slowly. Since most of the acreage is controlled in a large block by one company there has been no intensive competitive drilling. Approximately 8 producers and 16 dry holes have been drilled. Production is from the eastern equivalent of the Woodbine and Eagleford horizons of the Mexia district, and has been found extending in a northeast-southnlest direction across the River Neches on the southeast flank of the dome. One of the best wells, the T. H. Jones No. 2, had an initial production of 90 bbl. per hr., and others have made from 100 bbl. per day to 50 bbl. per hr., but production of the better wells has either been shut in or choked down to less than 2000 bbl. per day. At the end of the year the daily average, production was about 2500 bbl. from 8 wells. Considerable gas pressure is present and one well, the Elliot Clark No. 2, drilled in 1927, was shut in with an estimated wet gas production of over 5,000,000 cubic feet.

Jan 1, 1929

By R. P. Agarwala, M. S. Anand

Using residual activity technique, the diffusion of palladium, silver, cadmium, indium, and tin in alunzinum has been studied in the temperature range of 400" to 630°C. The diffusivities (in units of square centimeters per second) have been expressed as: IMPURITY diffusion in aluminum,1-9 silverand lead5 for cases of low solid solubility of the impurity in the host metal has yielded frequency factors in the range of l0-6 to l0-9 sq cm per sec whereas the activation energy is practically half the self-diffusion activation energy value. From the observed values of frequency factor, activation energy, and entropy of activation, it has been suggested' that these solutes are not diffusing by vacancy or interstitial mechanisms but by a mechanism which should be consistent with such low values of the diffusion parameters (Do and Q). However in spite of extensive work on these types of systems, the mechanism of diffusion is still not well understood. The present investigation on the diffusion of palladium, silver, cadmium, indium, and tin in aluminum has been carried out to throw further light on the diffusion mechanism in systems, where the solid solubility is very low (except for the case of silver). The results are discussed on the basis of solid solubility and the structural changes involved owing to the presence of the solutes in aluminum solid solution. An attempt has also been made to apply the existing theories of charge5-8 and size8 difference between the solute and the solvent. EXPERIMENTAL PROCEDURE Specimens (1/2 in. diam by 3/8 in. high) were machined out of pure aluminum (99.995 wt pct) rod obtained from Johnson Mattheys. They were sealed under vacuum in quartz tubes and annealed at 620° C for several hours; the grains thus developed were sufficiently large to eliminate the possibility of diffusion along the grain boundaries. The flat ends were prepared carefully after polishing as described previously,10 Radioactive nitrates of cadmium, indium, and tin and chloride of palladium containing, respectively, cd115, 1n114, sn113, and pd103 were dissolved in distilled water and mixed with 30 pct acetone. By means of a micropipet a drop of this solution was placed on a smoothly polished and lightly etched surface of the specimen. Due care was taken to see that the solution spread uniformly on the surface of specimen without trickling down its sides. Radioactive silver was elec-trodeposited using a AgCN-KCN bath. The amount of sample deposited in all the cases was not more than 0.1 µ thick. The samples were then sealed in quartz tubes in vacuum. The cadmium samples were sealed in a purified argon atmosphere to avoid evaporation. The samples were then diffusion-annealed. The temperature of annealing varied between 400° and 630°C and was controlled to ±5°C. On heating to -400°C,the deposits of cadmium, indium, and tin, which were of the order of 0.1 p in thickness, were converted to their respective oxides. The contribution of oxygen present in the lattice of aluminum due to these oxides has been calculated and found to be less than 10 ppm in all cases. Oxide method has already been used by other workers11'12 in diffusion studies without any controversy on the issue. However, in some of these investigations, metallic deposition was also tried. The diffusivities calculated from these measurements were found to agree very well with the diffusivities obtained by using the oxide method. Thus it is assumed that the measured diffusivities represent true diffusion coefficients. Since palladous chloride decomposes at about 500°C, the deposited samples which were to be diffusion-annealed below 500°C were heated in vacuum for a very short time at 500°C to allow the decomposition of palladous chloride to palladium metal. Time taken in decomposition of nitrates to oxides and chloride to metal was negligibly small as compared to the period of the diffusion anneals. The residual activity technique13 was used to study the diffusion profiles where thin layers from the specimen surface were removed by grinding it parallel to a flat surface on a 600-grade carborundum paper. The specimen was washed, dried, and weighed, the differ -ence of the weight being the measure of the thickness of the layer removed. After each such abrasion and weighing, the total residual activity on the surface of the specimens was measured by counting 0.656, 0.94,

Jan 1, 1968

By F. H. Gilpin

SINCE Noah pitched his ark within and without with pitch, the use of asphalt in human endeavor has been increasing-for Noah's pitch was asphalt. Asphalt is a bituminous material found in nature, either pure or admixed with smaller or greater quanti-ties of mineral and non-mineral materials, or obtained by the refining of crude asphaltic-base petroleum under proper methods of control. Native or "natural" asphalts are scattered through-out the world, though the commercial value of the various deposits varies greatly, depending upon both their accessibility and magnitude and the quality of the material found. It is an acknowledged fact that such asphalts have been produced through natural causes by practically the same application of tempera-ture and pressure as are used in the modern refining of crude asphaltic-base petroleum. The best known of all the native asphalt deposits are those of Trinidad Lake in the Island of Trinidad, British West Indies, and of Bermudez Lake in Vene-zuela. Asphalt from Trinidad Lake, after refining to remove organic and some inorganic diluents, contains approximately 35 per cent, of inorganic residue, and the asphalt thus produced must be fluxed with lighter asphaltic or semi-asphaltic base oil to make it com-mercially utilizable. The refined asphalt obtained from the Bermudez Lake deposit contains from 4 to 6 per cent. of inorganic material which cannot be removed. This asphalt, also, must be fluxed to produce com-mercial products. Small quantities of similar materials are available in other locations. The best pure native asphalt' is known as. gilsonite and is mined in com-mercial quantities in the State of Utah. In numerous places in the United States, particularly Oklahoma and Kentucky, there are deposits of sand¬stone and limestone impregnated with bitumen, which are known as rock asphalts. These rock asphalts may be used, particularly in the paving industry, either as found or by slight fluxing; from some deposits the asphalt is extracted and marketed commercially.

Jan 2, 1923

By W. E. D. Jr. Stokes

THE application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government records, 30. Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the rail-way at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a, community of 1000 whites have been transported by airplane. A 31..4-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo. Many large American oil companies operated fleets of planes during 19:36, ranging from fast, luxurious air liners for executives to elaborate geological prospecting units, ambulance planes, freight carriers and pipe-line repair crews. According to the U. S. Geological Survey, commercial firms photo-graphed 16,291 square miles during 1935, while the Government compiled from aerial photographs by the Geological Survey in the United States 85,544 square miles. It was found that information could be determined in a fraction of the time required by surface methods.

Jan 1, 1937

By A. W. Griffith, R. G. Beverly, W. A. Millsap

THE Grand Junction Pilot Plant, operated by National Lead Co. Inc., for the U. S. Atomic Energy Commission, is engaged in the amenability testing of orebodies to establish design and cost data for commercial mills and to test new processes for recovery of uranium from ores. Test work was performed to study the effects of several variables on leaching of uranium ores in carbonate solutions. Many of these variables had been investigated in the laboratory, but pilot plant tests were desirable to evaluate their importance in semi-works equipment and to predict optimum operating conditions for future commercial mills. The results of these tests should serve as a guide in selecting the most efficient and economical method of leaching uranium ores amenable to a carbonate process. This article is concerned with a process in which uranium is extracted from the ore by a hot Na2CO3- NaHCO3 solution; the uranium-bearing solution is separated from the solid residue by filtration, and uranium is then precipitated by chemical means.

Jan 9, 1957

By L. VOGELSTEIN

OUTSTANDING among the year's events in copper has been the reimposition of an import duty of 4r. per pound in this country which became effective June 21. In consequence of this action by Congress, the Ottawa Empire conference recommended a duty of 2d. per pound equivalent at normal rate of exchange to our 4c. duty, on all copper originating outside of the Empire. Lip to the middle of this year only Russia and Japan had a closed market; the import duty on copper in Russia is 30 per cent ad valoremm and in Japan about 2c. Russia's consumption has always been in excess of production and she has imported from 2(1,000 to 40,000 ton, of copper per annum. Japan, with a production of 6,000 to 7,000 tons per month, has absorbed, in normal times, its production, but during recent: sears has exported varyiug quantities in 1929. 2,200 ton-: in 1930, 2,700 tons, and in 1931. 3,600 ton-. Aside from the-e two countries, the international market has heretofore been free. It and when the British Empire duty become, effective the world's markets will be divided into four unit: 1. Russia and Japan, 2. United States. 3. British Empire. 4. Rest of the world. The world's production at present is rennin it the rate of 930.000 tons per annum. This year's production will be over 1,000,000 tons because the several curtailment did not become effective until the second quarter. consumption will be slightly in excess. Deducting from 30,000 tons Russia's and Japan's production of 121.000 tons, 806,000 tons is left divided a, follows:

Jan 1, 1932

By J. H. Palm

Experiments have shown12 that the formula -S = St - (St - Se')e ne [1] expresses very well the relation between the true stress S and the true form monotonic deformation of plastic metals in single tension and compression (Fig 1). St (asymptotic or final stress), Se' (threshold stress) and ne (characteristic or specific strain) are constants, the significance of which immediately follows from Fig 1. Only at the initial stages of deformation the experimental curve runs below the theoretical curve. This may be due, at least partly, to the uneven stress distribution caused by the anisotropy of the crystals. It is now obvious that a similar formula H = Ht- (Ht- He)e ne' [2] might be valid for the relation between the hardness and the strain. The hardness can be only a function of the strain and must therefore be independent on the hydrostatic tension present in the neck during straining. Hence, if Eq 2 is correct it will also represent the relation between hardness and strain in the middle section of the neck, the strain of which is generally assumed to be almost or fully homogeneous. For aluminum, copper, and several copper alloys it is indeed observed that Eq 2 agrees very well with the experimental Vickers hardness-strain relation from zero strain on up to the strain at fracture. Moreover nc' is, for several metals fairly equal to nc- Hence H = C1 + C2S [3] C1 and C2 are constants during uniform uniaxial tension. Eq 3 was also obtained for copper by Voce.3 According to Hencky's theory4 the ratio of the Brinell or Vickers hardness and the yieldstress (expressed in kg per mm2) of a non-strainhardening metal is approximately equal to 2.8. If Eq 1, 2 and 3 are correct the ratio Ht/S, must accordingly be the same for all plastic metals and be equal to 2.8. It is now experimentally established that this ratio varies between 2.7 and 3.1 with a mean value of 2.9. Taking into account that Ht and especially St can be obtained only by extrapolation from the range of rather low strains, the agreement with the theory is very satisfactory. References 1. J. H. Palm: Appl. Sci. Res. Al (1948) 198. 2. E. Voce: Jnl. Inst. of Met. (1948) 74, II, 537. 3. E. Voce: Metal Treatment (1948) 15, 53. 4. H. Hencky: Zlsch. f. angew. Math. and Mech. (1923) 3, 241.

Jan 1, 1950

By J. E. Hanafee, G. J. London

MANY studies of the deformation behavior of materials under a superimposed hydrostatic pressure have shown that materials brittle at ambient pressure behave in a ductile manner under pressure. Thus, with a metal such as beryllium which possesses relatively low ductility, but otherwise exhibits quite useful physical and mechanical properties, hydrostatic pressure may be particularly useful for both forming beryllium shapes and studying its deformation behavior. In fact, it has been found1"4 that polycrystal-line beryllium in both ingot and powder form appears to behave in a more ductile manner on a macroscopic level in a hydrostatic pressure environment, and it has been suggested2 that this is due to activating a new slip mode. Furthermore, Andrews and Radcliffe5 have found pressure induced nonbasal dislocation activity in hot pressed beryllium. Recently6 it has been shown in "c-axis" compression tests under hydro-static pressures up to 28 kbars that the shear stress needed to cause slip with a Burgers vector out of the basal plane (pyramidal slip) does not change with increasing pressure in beryllium with a purity of some 99.5 pct. This material is equivalent or more pure than the beryllium used in the previous pressure studies. Thus, it appears, as suggested by Inoue et al.,3 that the hydrostatic pressure affects the fracture stress rather than the stress necessary to activate pyramidal slip in beryllium. However, in "c-axis" pressure tests on high purity 12 zone pass beryllium (˜50 ppm total impurities) the macroscopic compression stress needed to cause pyramidal slip was considerably lower than that at ambient pressure.6 It has further been shown that alloying beryllium with nickel and copper in the range 2-5 wt pct also favors the occurrence of pyramidal slip in "c-axis" compression tests,7'8 while lower amounts of nickel and copper do not have significant effects. In the present study the combined effect of hydrostatic pressure and alloying high purity beryllium on the shear stress needed to cause pyramidal slip has been ascertained. A 2.5 wt pct Cu alloy was selected as the first alloy to study as this level of copper did favor pyramidal slip at room pressure. A high purity (12 zone pass) single crystal of beryllium 0.3 by 0.1 by 0.1 in. was cut and polished by an orientation and lapping technique8 so that the top and bottom compression surfaces were parallel and within 3 min of arc to the (0001) plane and the sides parallel to the {l010} and {ll20} planes. In these compression specimens, therefore, the resolved shear stress was nearly zero on both the basal and prism planes, and slip was restricted to pyramidal systems. Analysis of slip traces on the two lateral surfaces served to accurately identify the active slip planes.6'9 The pressure unit was a modified piston-cylinder device fitted with a manganin transducer coil arrangement which continuously monitored and recorded the hydro-static pressure. The load on the specimen was measured by a strain gage load cell which operated entirely within the pressure chamber. This load cell was calibrated before and after each pressure cycle at room pressure in situ and the calibration did not vary more than ±1 pet. These techniques and devices have been previously described in more detail.6 Successively higher compressive stresses were applied to the single crystal under a superimposed hydrostatic pressure until fracture occurred. The strain rate was (4.5 ± 2.0) x 10-6 sec-1 and the average rate of pressure application and release was approximately 0.3 kbars per min. As the load on the specimen was applied by the piston which was used to increase the hydrostatic pressure, the pressure increased during the compression test. This increase ranged from 0.0 to 0.8 kbars, and the maximum hydrostatic pressures are quoted in Fig. 1. The lateral surfaces of the specimen were examined in a light microscope after each pressurization/stress cycle so that the stress at the onset of {1122} pyramidal slip could be ascertained. Post compression height measurements allowed the plastic strain in the specimen to be evaluated to within 0.03 pct. The resulting compression stress-plastic strain curve is shown in Fig. 1 with results of a "c-axis" test on a similar Be-2.5 wt pct Cu single

Jan 1, 1970

By Robert F. Mehl

THE mechanical behavior of metals and alloys is presumably conditioned by two factors; namely, the crystalline symmetry and the interatomic forces. Considerable attention has been given to the first of these factors through the recent advances in X-ray technique. It is the purpose of the present paper to call attention to the importance of the second of these factors, to point out promising methods of investigation, and to present some pertinent data. Plastic deformation takes place by slip along atomic planes.1 This slip may be inhibited in a number of ways: by the interatomic forces of cohesion which bind the atoms rigidly in a lattice structure, which in pure metals is usually of high symmetry; by lattice distortion caused by solid solution formation or by mechanical strain; by the intercrystalline boundaries where slip is restrained, probably by the non-registration of the atom planes in adjacent crystallites;2 and by the presence of small hard particles which serve to "key" the slip along the atom planes.3 In pure metals, and perhaps also in solid solutions, the atom planes of easiest slip are those exhibiting the greatest density of atomic population and the greatest interplanar distance4 and apparently can now be predicted from the analysis of the lattices. Concerning the interatomic forces, which resist this slip by holding the atoms firmly together, little is known. Most textbooks on physical metallurgy, following the work of Bottone,5 correlate the hardness of the pure metals with the atomic volume,

Jan 1, 1928

By E. R. Gilbert

Klopp et al. have reported data on tensile and creep properties of are-melted and electron-beam-melted tungsten. We would like to point out some similarities between their creep results and ours on are-melted and powder-metallurgy tungstenand offer some alternate interpretations of the data which lead to different rate-controlling mechanisms. Klopp et al. observed extensive transient creep in the 2250" to 3500°F temperature range where the acthetivation energy is 106,400 ± 3300 cal mole-1. They suggest cross slip as the possible rate-controlling mechanism since "cross slip may occur only by the movement of screw dislocations, and not edge dislocations, thus allowing only partial recovery of the strain hardening and resulting in a continuously decreasing creep rate, characteristic of transient creep.'' Our tests on are-melted tungsten and powder-metallurgy tungsten displayed an extensive transient creep stage in the same temperature range but they also displayed a steady-state creep stage. The stress levels and strain rates of the two investigations, 1.4 to 7 kg mm-2 and 10-7 to 10-4 sec-1 for that of Klopp et al. and 4.5 to 10 kg mm-2 and 10-8 to 10-4 sec-1 for those of Gilbert et al., are overlapping. The activation energy for creep of our powder-metallurgy tungsten is 105,000 cal mole-1. This close agreement with the value found by Klopp et al. suggests that the same mechanism may be common to both types of materials. It may be possible to gain some additional insight into the rate-controlling mechanism by applying the analysis made by conrad22 in terms of the activation volume. The value for the activation volume depends upon the dislocation mechanism and may be used to help differentiate between various dislocation mechanisms. The activation volume for cross slip is 10 to 100 b3. Values determined from our data were 130 to 220 b3 which are in better agreement with the range of 102 to 104 b3 for nonconservative motion of jogs. Values determined from data of Klopp et al. are 240 to 1040 b3. We suggest that the rate-controlling mechanism for creep in this temperature range may be nonconservative motion of jogs assisted by enhanced diffusion along grain boundaries or dislocations. This model requires an activation energy lower than that for self-diffusion as is observed. If this is the controlling mechanism, a higher activation energy which is closer to that for self-diffusion might be expected for tests conducted on specimens with reduced grain boundary area, i.e., larger grain size. In support of this premise we have conducted tests on speci- mens having one to three grains per cross section for which a higher activation energy of 130,000 cal mole-1 was observed. Also, in agreement with results of Klopp et al., a faster creep rate resulted from the increased grain size and probable decreased dislocation density. Further argument against the cross slip mechanism is based on the constant activation energy we obsserved over the range of 5.0 to 10 kg mm-2,21 whereas the activation energy for cross slip displays a significant stress dependence.23 In addition to this, the powe on the stress term for the strain-rate dependence appears too high for cross slip. The values for tungsten fall in the range of 4.5 to 7 (Klopp et al. and Ref. 21) whereas values of approximately 2 are observed in creep by cross slip for hep metals.24 At temperatures from 3300° to 4000°F, Klopp et al. observed an activation energy of 141,000 ± 4000 cal mole-' which is less than that for self-diffusion, 153,000 cal mole-1, 25 and less than that reported for high-temperature creep of powder-metallurgy tungsten by Green:' 160,000 cal mole-1. Klopp et al. suggested that recovery of strain hardening by dislocation climb is the rate-controlling mechanism in this temperature region. Actually an activation energy larger than that for self-diffusion is predicted by this model if the temperature dependence of the elastic modulus27 is taken into consideration. Klopp et al. attributed this lack of correlation to the compositional differences between powder-metallurgy tungsten used by Green and their own arc- and EB-melted tungsten. It is our position that the value of 141,000 ± 4000 cal mole-' represents a transitional value between the higher and lower activation energies and does not represent a discrete mechanism of deformation. If the tests had been extended to higher temperatures the higher value of activation energy would have been observed as has been demonstrated by both our analy sis'' of isothermal test data by GE-NMPO28 and differential temperature tests28 on are-melted tungsten. The activation energies determined (170,000 and 160,000 cal mole-1) were greater than that for self-diffusion and are in better agreement with the value found by Green. The model of dislocation climb is associated with ; activation volume of 1 b3 according to Conrad.22 The activation volume calculated for the creep data of fou independent investigators in the temperature range where the activation energy for creep is near that for self-diffusion (Klopp et al. and Refs. 26, 28, and 30) is 110 to 2800 b3 and is in the range suggested for nonconservative motion of jogs. In the case of tungsten this mechanism may be preferred over that of dislocation climb. Sincere appreciation is expressed to Messrs. J. E. Flinn and F. L. Yaggee for the helpful discussions and suggestions in the preparation of this communication.

Jan 1, 1967

By T. S. Lundy, R. E. Pawel, F. R. Winslow, C. J. McHargue

The volume-diffusion coefficients of Nb-95 and Ta-182 in niobium have been measured over the temperature range 878° to 2400°C. High-temperature specimens (T 21500°C) were sectioned by conventional lathe and grinding techniques while low-temperature specimens were sectioned by an anodizing and stripping technique previously described. Over a range of more than ten orders of magnitude in diffusivity, the self-diffusion data is well-represented by the equation: D = (1.1+ 0.2) exp [- (96,000 * 900)/RT ] cm2/sec Upward deviations from this line are explained by short-circuit diffusion in combination with the loss of resolution of the sectioning techniques. Oxygen contamination within the range 100 to 450 ppm was found to have little or no effect on the self-diffusivitj 01 niobium. In a limited number of measurements, the diffusivity of Ta-182 in niobium was found to be about half that of Nb-95 in niobium. These data may be described by D = (I.0+0.90.5)exp [- (99,300 * 2400) /RT ] PREVIOUSLY reported studies of self-diffusion in niobium were by Resnick and Castleman1 and Peart, Graham, and Tomlin.2 The data of Resnick and Castleman over a temperature range 1585" to 2120°C show considerable scatter but. can be represented by D = (12.4 *0.8) exp [-(105,000+3OOO)/RT] cm2/sec The limited data of Peart, Graham, and Tomlin follow the equation D = 1.3 exp (-95,00O/RT) cm2/sec In view of recent diffusion data for ß zirconium3 and 0 titanium4 in which Arrhenius-type plots do not yield straight lines and of the potential high- temperature uses of niobium and its alloys, we thought it important to investigate the diffusion behavior of this bcc refractory metal over a large temperature range. This has recently been done for molybdenum,5 chromium,6 vanadium,"" and tantalum.9 Niobium was a particularly suitable material for this study largely because of the development of an anodizing and stripping sectioning technique which enables diffusivities as small as l0-19' sq cm per sec to be determined accurately.10 In addition to self-diffusion data, data were obtained for the diffusion of Ta-182 in niobium and for the effect of varying oxygen content on self-diffusion. I) EXPERIMENTAL PROCEDURE Materials. The niobium was obtained from three sources: 1) melting stock from Shieldalloy Corp., 2) electron-beam melted single crystals, 1/2 in. diameter, from Semi-Elements, Inc., and 3) oxygen-doped, electron-beam melted single crystals from Materials Research Corp. The melting stock was electron-beam melted and specimens 5/8 in. diameter by 1/2 in. long were machined from the center of the bar. The analysis supplied by the vendor and an interstitial analysis of one of the specimens are given in Table I. The single crystals (type 2 above) were cut with a jeweler's saw to specimens about 3/8 in. long. The interstitial analysis of this material is given in Table 11. This material was used

Jan 1, 1965

By Harry L. Washburn, Robert L. Llewellyn, W. J. Halvorsen

Many of the problems that occur in the preparation plant originate from practices in the mine. Impurities in raw coal can be in the seam itself or from extraneous material taken in mining from the roof or bottom. In the case of underground mines, the choice of mining equipment will affect the size consist and the amount of extraneous material included with the coal. Also, governmental regulations concerning the degree of rock dusting, gobbing underground, and cleanup have increased the dirt in raw coal. Sulfur dioxide emission standards, on the other hand, are pressuring the coal industry to clean coal more thoroughly. Coal supplied for coking purposes is nearly all upgraded by washing, while for the largest market, electric power generation, a high proportion is shipped as a raw product with processing, in whole or in part, only necessary when excess impurities are mined with the coal. This chapter will deal primarily with plants that process or wash coal to some extent (Fig. 1) and only incidentally with mines shipping raw run-of-mine coal crushed to a top size of, usually, 51 to 102 mm (2 to 4 in.), with little, if any, other treatment. JUSTIFICATION FOR COAL PREPARATION During the past decade, major changes have occurred affecting the market, profit, and long-range planning of the coal industry. Mining companies have become "partners" with consumers at many new and some old mines, both for steam and metallurgical coals. Coal properties have become "assigned" tonnages at mutually agreed upon conditions and prices. Lower unit-train tariffs have been instrumental in helping coal markets to compete against oil and nuclear energy. Coal prices for power plants are still on a Btu (British thermal unit)

Jan 1, 1981