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By F. M. Smith, R. H. Moore, J. R. Morrey

Electrodiffusion in y cerium reported by Henrie has been confirmed and a Preliminary estimate made of the relative rates of electrodiffusion of iron, cobalt, and nickel. These diffuse to the anode at rates decreasing in that order. In addition, copper and manganese exhibit slow, but detectable, diffusion to the anode and molybdenum exhibits detectable diffusion to the cathode. The electrodiffusion of carbon, .zirconium, antimony, magnesium , and silicon in y cerium could not be detected. Iron and cobalt diffuse in y cerium at rates proportional to the current density and with no apparent dependence on temperature. Decreasing polarization of iron and cobalt with increasing temperature, which cancels the expected rate increase, would account for this behavior. The electrodiffusion rate of iron in y uranium and in E plutonium has been measured. Diffusion of iron is anode-directed. Tin was found to diffuse to the cathode, in y uranium, at an appreciable rate. In all of these solvent metals, negative ions diffuse to the anode and positive ions to the cathode. The potential field effect appears to account satisfactorily for these results. FROM early experimental work summarized by Jost1 and Seith,2 the driving force for electrodiffusion was attributed to the potential field acting on ions in a metal. More recently, Heuman,3 Wever,4 and Huntington5 have shown that momentum interchange between conduction electrons and mobile entities in the metal contributes to electrodiffusion. Electron momentum interchange is anodically directed and the direction of diffusion resulting from the field force is dependent upon the charge on the diffusing entity. These two effects may either reinforce or oppose each other. Glinchuk6 has pointed out that momentum transfer in defect conductors should be cathode-directed and this appears to be the case as demonstrated by wever's4 work on iron. Barnett's7 work, on the other hand, indicates that, even in defect conductors, electrons show a negative E/m ratio when accelerated with respect to the lattice and should lead to anode-directed momentum transfer. In discussing this problem, Wever and seith8 suggest that defect electrons interact preferentially with activated ions so as to allow a net movement toward the cathode while still maintaining an electron momentum transfer in the anode direction. Williams and Huffine9 and Henriel0 have demonstrated that electrodiffusion may be useful for purification of yttrium and cerium. In yttrium, Williams and Huffine note that movement of several metallic impurities toward the anode is in keeping with observations in most other metallic systems and indicates that yttrium remains a normal electronic conductor at least to 1230°C. Close inspection of their data shows, however, that oxygen, nitrogen, and the transition elements diffused toward the anode, while nontransition elements diffused toward the cathode. This suggests that potential field effects may have been appreciable. The present work was concerned with the applicability of electrodiffusion as a technique for purification of plutonium, but, because of the obvious hazard inherent in work with this metal, experiments to develop the technique were carried out using cerium and uranium. The results of electrodiffusion measurements on these metals and on plutonium are reported here. EXPERIMENTAL The metal specimens prepared for this work were 6 in. long, 1/4 to 1/2 in. wide, and 1/16 to 3/32 in. thick. The uranium specimens were machined from a bar which analyzed 310 ppm Fe and the electrodiffusion of iron was followed by spectrographic and by chemical analysis. Cerium and plutonium specimens were cut from sheet rolled from ingots obtained from molten salt-metal equilibrations during which radioactive tracers were introduced. The electrodiffusion of the tracers was subsequently determined by counting methods. The specimens were electrolyzed between nickel electrodes containing resistance heaters used to equalize the specimen and electrode temperatures, thereby reducing thermal gradients. The temperature of the electrodes adjacent to the ends of the specimen was measured with chromel-alumel thermocouples which were connected to the heater controls. The surface temperature of the specimen at a point midway between the electrodes was measured with a sapphire rod pyrometer, the output of which controlled the dc power supply. This assembly was enclosed within an evacuable chamber containing a quartz viewing window. The temperature of the specimen over its entire length could be scanned with a portable pyrometer through

Jan 1, 1965

By R. J. Wasilewski

The variation of elastic modulus with terrzperature between -150° and 600°C has been investigated. Compounds close to equiatomic cornposition exhibit very low modulus values and very high damping near room temperature. The modulus rises steeply with both decreasing and increasing temperature. The modulus minimum and the high damping are believed to be connected with a martensitic transformation of TiNi. In bulk material this transition takes place slightly above room temperature quite rapidly and reversibly, with a hysteresis of some 30°C, depending on the Ti:Ni ratio. Oxygen impurity affects the reaction time. THE inter metallic compound TiNi has been reported to exist in an ordered CsCl (B2) structure,l-6 the homogeneity range varying rather markedly with temperature.7 Some investigators reported this compound to decompose peritectoidally to Ti2Ni and TiNi, between 650° and 800°C,3 or below,',g the latter workers also suggesting the decomposition to be strain-sensitive. Purdy and Parr were the first to report a structural transformation to a new, possibly hexagonal, structure at 36°C,7 a temperature indubitably too low to allow the significant amount of diffusion necessary for a peritectoid reaction. Mechanical-property investigations of compositions close to TiNi just above room temperature have qualitatively shown remarkable anomalies, particularly with respect to clamping,' and to a "memory" effect, that is, plastically deformed material returning to its original shape on being heated through the "decomposition" temperature.9 The original explanation of this effect—based on the apparent experimental observation of Ti2Ni or TiNi, formation in the material subjected to tensile or compressive stresses, respectivelp—does not appear plausible. It appeared more probable that the change involved may be a martensitic, diffusionless structural transformation, similar to those observed in other B2 structures such as 0 brass,'' AuCd,ll and AuZn.12 The existence of such transformation has been established recently,', although the symmetry of the low-temperature structure is not yet known. The present paper describes the elastic modulus and damping behavior of polycrystalline TiNi in both structures. EXPERIMENTAL METHOD 1) Specimens. All the specimens to be investigated were prepared from premelted electrolytic nickel and iodide titanium by nonconsumable arc melting and casting in a water-cooled copper mold. The cast billets were canned in mild steel, extruded, and swaged to approximately 0.375 in. diam. The cans were then removed by pickling or machining. Preliminary material balance checks indicated no significant weight losses on melting (less than 5 mg on a 50-g button); hence nominal compositions have been used throughout. In agreement with previously reported observations7 no single-phase material was obtained at—or close to—Ti 1.00 Ni1.00 a small amount of finely divided second phase always being present. It was found that most of the oxygen impurity was associated with this minor phase, which was identified as oxygen-bearing Ti2Ni—possibly Ti,Ni,O. The amount of this phase—at any given Ti:Ni composi-

Jan 1, 1965

By H. D. Hoskold

This paper is presented in fulfillment of the promise made in my paper, " Remarks upon Surveying-Instruments,"" etc., and much of the material which would constitute an appropriate introductioil here is omitted, because it has been already published by the Institute, in connection with my own contributions- or those of Mr. Scott and others, in vols. xxviii. to xxxi. of the Transactions, and in the special Institute volume on Mine-Surveying Instruments. In these preceding publications will be found, for instance, descriptions of the writer's " miner's transit-theodolite" of 1863,† and his later " angleometer,"‡ both of which were steps of the progress in engineering instruments and methods which originated in the work of Bourns, before 1842, on the " BoxTunnel " of the Great Western railway in England, in which he had to make connections by direct telescopic sights down the shafts. About 1870 the writer devised a practical and much superior plan, and made detailed drawings for an instrument to meet all the conditions he had proposed prior to that year. The detailed plans were communicated to a celebrated optical firm in London; but, owing to their loss (in Paris or Germany, it is believed) and to other reasons, the matter was, for the time, allowed to lapse. Following upon Bourns's idea, my friend, the late Mr. Beansland, introduced, in 1856, a new system and a portable astronomical instrument.§ Such instruments, however, were neither common nor convenient, and did not come into general use among engineers.

Jan 1, 1902

By S. P. Kinney, A. J. Boynton

THIS paper is not the result of recent research with regard to any particular feature of iron metallurgy, blast-furnace practice or mechanical engineering. It is rather a series of notes with regard to contemporaneous progress in blast-furnace construction and operation, together with some suggestions as to changes and improvements that seem to be desirable. On April 1, 1930, a committee of the Chicago District Blast Furnace and Coke Association presented to that association a rather ambitious study of blast-furnace equipment, together with recommendations for the design of construction of a complete blast-furnace unit for the production of 1000 tons of pig iron per day. This report represented the result of months of study by members of the committee, all of whom were actively engaged in operation or design of blast-furnace plants. It is natural, therefore, that comments on the present state of the art should take this 1000-tons furnace, as recommended by the Association, as a basis for comparison with corresponding features of construction or design. See Table 1. In looking through this report at the present time, the significant difference is in the nature of the gas-washing equipment that today would be specified. In other respects, the installation would remain generally very much as it was outlined in 1930. The change in furnace dimensions would be very slight and of no especial significance, except with respect to changes in stock-line diameter, of which more will be said hereafter. The high-efficiency stove as developed by various designers is thoroughly described within this report, and few changes have taken place since. Blowing equipment shows refinement and reflects the improvement in steam engineering. Hoisting and charging equipment and ladles for the conveyance of iron and slag remain, in general, as they were in 1930. In accordance with a general tendency

Jan 1, 1935

By Richard S. McCaffery, Joseph F. Oesterle, Oscar O. Fritsche

The method of obtaining the data on which this paper is based is explained in detail in the paper on Determination of Viscosity of Iron Blast-furnace Slags.' The work was made possible by a grant of funds from Engineering Foundation, and it gives the results now obtained, continuing the general subject of our previous work and reported in former papers2 The data experimentally obtained are in the form of a temperature-viscosity curve for any slag of particular composition. (See Fig. 1.) From these curves, the viscosity of a slag of a definite composition and at a definite temperature is taken off and is plotted on a plane triaxial diagram showing compositions of silica lime and alumina on a plane representing constant-magnesia content (Fig. 4). The temperatures at which these results were plotted are 1300°, 1350°, 1400°, 1450°, 1500°, 1550" and 1600" C. and since the constant magnesia plane sections were an even 1 per cent. magnesia apart, magnesia analyses not of even unit magnesia composition were projected to these even unit magnesia planes. For example, 1.78 per cent. magnesia and 2.35 per cent. magnesia were projected to the 2 per cent. magnesia plane. The triaxial diagrams on which this first plotting was made were drawn on celluloid sheets, a transparent material on which it was easy to draw. When all the experimental work was plotted on celluloid in this way, the sheets representing a definite temperature were stacked in the proper order and were examined by transmitted light. Where

Jan 1, 1932

By William Phillips

THE possible sources of potash salts in the United States have been considered from many points of view during the last several years, but it is only within the last two or three months that the situation has become acute. We import from Germany, the only source of large supply, more than $10,000,000 worth of potash salts annually, and this business has been badly crippled by the European war. If there was ever a time in our industrial existence when the necessity of providing for our own needs was more acute than it is now, we are not aware of it. One has only to study the price, lists of chemicals sent out by the large supply houses to see the change wrought within a very short time. Whether or no these prices are to maintain for a considerable time, no one can say; but it appears to be probable that we shall not see prices materially lower for a period of uncomfortable length, to say the least. It is not my purpose at this time to discuss the various sources of supply of potash salts that have been suggested or recommended. Some of them might afford a pleasing relief but all of them combined would not affect the situation seriously. If we are to have our own sources of potash salts, they will have to compare, in some efficient manner, with the sources upon which we have drawn during the last 20 or 30 years; i.e., they must exist-in minable quantities. It seems to me to be quite idle to speculate upon our domestic sources of potash if those sources are not of a character similar to those upon which we have so long depended. A few thousand or, perhaps,, a few hundred thousand dollars' worth of chemically derived 'potash may be produced under the stress of present conditions, but when we consider that each year demands more than $10,000,000 worth, we must look to underground sources; we must look to mines similar to the famous Stassfurt and Halle deposits. If we cannot mine potash salts, we shall have to do without them for a while.

Jan 2, 1915

By F. C. Kelley, L. L. Wyman

In order to clarify and amplify the existing data concerning the action of the cementing material in cemented tungsten carbide alloys, the authors have initiated this investigation of the entire range of cobalt-tungsten carbide alloys. Inasmuch as the ultimate objective is relative to what actually goes on during the sintering of cemented tungsten carbide materials, this work was necessarily restricted to heat treatments similar to those used in actual production of these materials. In the course of numerous experiments, the authors have noted several conditions that indicated that there was a solubility to be considered. Among these factors are the following: 1. Many of the alloys showed a much larger amount of binding constituent to be present than could possibly be accounted for by the cobalt content. 2. In many areas, grains of the carbide constituent are much larger than the particles of carbide originally added. In addition, these grains are of very regular contour. 2a. In samples of cemented tungsten carbide which had been fused in the atomic hydrogen torch in the presence of excess binder constituent, immense grains are formed, and their shapes are very regular. This is also true when the cemented tungsten carbide of 13 per cent. Co content is fused alone in the atomic hydrogen torch. Contrary to general expectation, chemical analysis of this material, after fusion in the atomic hydrogen torch, checks the analysis of unfused material. 3. In making the cemented tungsten carbide materials by the process of exerting the pressure at the time of heating a certain portion of the ' contents squeezed out of the mold. Chemical analysis has shown that this material contains approximately 12 to 20 per cent. of tungsten. The microstructure shows a cored dendritic structure interlaced with eutectic network, and some graphite, as shown in Fig. 1. 4. Thermal analysis of these materials has consistently indicated an arrest point close to 1350" C.

Jan 1, 1931

H. H. Kellogg (Columbia University)—The accurate measurements of the equilibrium gas ratios for the reaction: Pb(1) + H2S = PbS(c) + H2 [I] reported in this paper are a distinct contribution to the literature, and the authors are to be congratulated. I wish to comment, however, on the correlation of the data which is presented. The authors show a straight line correlation of log H2S/H2 vs 1/T, Fig. 1, and are satisfied with this for calculation of ?Fo even when extrapolated to low temperature (427 °C). Heat capacity data for the constituents of this reaction are available (at least to 900°K), however, and ACP for reaction [I] is finite and positive in the temperature range studied. Simplification of the heat capacity equations yields: ?CP= 2.71 + 1.65 x 10-3T (298°-900°K) This positive value of ?CP should result in a small but noticeable curvature of a plot of log K vs 1/T. That the experimental data fail to show such a curvature may be traced to another oversimplification of the author's treatment of their data. They assume that the activity of liquid lead is unity for all temperatures, so that

Jan 1, 1961

By Peter Tegart

The discovery of gold in the Toodoggone River area is credited to Charles McClair who mined placer deposits in 1925, reportedly valued at $17,500. After he and his partner went missing in 1927, efforts to relocate their workings resulted in the formation of Two Brothers Valley Gold Mines Ltd. in 1933, in which the legendary Grant McConachie (first president of CP Air) played an active role. This was the age when the prospector first utilized the airplane to reconnoitre remote areas. What greeted the observer from the air was an area rich in orange and yellow colours characteristic of gossans formed by the oxidation of sulphides. However, Samuel Black, a Hudson Bay Company fur trader, had also noted in his diary as early as 1824, the unusual and many gossanous colours in the headwaters of the Finlay River. These gossans, coupled with white limestone bluffs and the presence of placer gold, attracted the first reconnaissance of the area by Cominco in 1929. Cominco was ever active in remote areas at this time. They staked and worked several base-metal showings hosted by limestone at the margins of intrusive stocks. These early workers also obtained erratic high gold assays from chalcedony float samples found in creeks draining into the Toodoggone River. However, because the samples gave inconsistent assays, no concerted effort was made to locate their source. Except for the occasional horse-supported prospecting party of the late 1940s and early 1950s, the area did not receive much attention until 1968. Work until this time focused on the base metal lead-zinc showings which contained attractive silver credits. Gold was not an attraction because of the set price established by the US government. The late 1960s saw the northward expansion of porphyry copper exploration into the Toodoggone. A program of gossan soil sampling (gossans which had attracted the early workers) was carried out by Kennco Explorations (Western) Ltd. in 1966-1967. They analysed for base metals in the field, using a cold extraction method. The Kemess copper- gold prospect was staked as a result of anomalous copper values from this early geochemical program. In 1968, Kennco continued the program of silt traversing and field geochemical testing. The samples were further subjected to multielement analysis consisting of copper, molybdenum, lead, zinc, cobalt, nickel, and silver at Kennco's North Vancouver laboratory. Several anomalous creeks, high in combinations of copper, molybdenum, and silver, were outlined. Some initial soil grids were also established. The fall of 1969 saw the return of Kennco prospector Gordon Davies and geologist Bob Stevenson to check out a well-defined molybdenum, scattered copper and silver anomaly in soils from a grid on the Chappelle claims. The subsequent analysis of several selected quartz felsenmeer floats yielded one assay which ran in the order of 0.25 kg/t (8 oz per st) gold and 2.2 kg/t (70 oz per st) silver. Subsequent trenching on the Chappelle claims exposed the source of float in a 4- m (134) wide vein of high grade gold-silver mineralization. These results led quickly to the realization that the district had precious metal potential. Subsequent exploration in the period 1969-1974 by Kennco resulted in the discovery of most of the gold and silver occurrences on the Chappelle and Lawyers properties. Several other gold and silver occurrences were found in this district by Cordilleran, Cominco, and Sumitomo, working the district during this period. Conwest optioned the Chappelle in 1973 and explored underground by adit entry as part of a one-year program. In 1974, Du Pont of Canada Exploration Ltd. optioned the Chappelle claims and in March 1980, using reserves developed on the A vein, placed the Baker mine into production at a rate of 90.7 Vd (100 stpd). The Amethyst zone on the Lawyers property, 8 km (5 miles) north of Chappelle, was found in 1973 by Kennco using continued, persistent followup prospecting of silver silt geochemical anomalies. A silt anomaly in the order of 3.4 ppm silver occurred in a stream flowing 300 m (984 ft)

Jan 1, 1985

By Frank Feuille, Edward Schuster

As the time allotted is short, we can present only a general idea of the oil laws in the Latin-American republics, as a supplement to Bulletin 206 of the Department of the Interior compiled under the direction of J. W. Thompson of the Bureau of Mines and entitled "Petroleum Laws of All America." We shall not discuss the European colonies in Latin-America nor the island republics. As to the countries discussed, we shall attempt to give the main features of such special petroleum legislation as has been adopted prior to the early part of this year; where no special petroleum laws exist, we must look to the mining codes for light on the petroleum policy. As the laws and regulations for the extraction of the metals are often difficult of application to, and are lacking in many essentials for, the petroleum industry, it is best for persons or companies desiring to enter, on a large scale, into the petroleum exploration and development of countries not having special petroleum legislation, to obtain a concession contract from the executive of the country under consideration, and to have the concession approved by the congress. If this concession, which would then be a special law, contains nothing contrary to the constitution of that country and does not infringe on vested rights of third parties, it should be reasonably safe. If in such country there is some doubt as to whether the petroleum subsoil is owned by the nation or the private surface owner, only public lands should be covered with the concession. Guatemala is the only republic in the group that discriminates directly against foreigners. Bolivia, Ecuador, Mexico and Venezuela require waivers of diplomatic protection.' Colombia requires foreigners to agree to be bound by its alien law. In addition,Mexico makes it unlawful for foreigners to acquire direct ownership of real estate, including mines, within a zone of 50 km. along the coasts and one of 100 km. alongitsland

Jan 1, 1923

Coal was known in this county before 1819, but there is no record of its use before that year. In that year a furnace, the first one built in the northwestern countries, was put in blast on Bear Creek; it was built to use coke and its first blast was with this fuel, which was made in heaps, but the blast was too weak and the furnace chilled after two or three tons of iron had been made. Charcoal was then substituted, and this use of coal ceased.1 In November of the same year a resolution was adopted urging state aid for a road from Kittanning to. Hamilton, New York: "that this road will increase the trade and industry of the whole county, between Pittsburgh and the New York line; and that our soil will in consequence be better tilled, our mines of coal, of iron and of salt, be better wrought, etc."2 In 1828 an advertisement of lands situated near Freeport on the Allegheny River and contiguous to the canal nearly completed between the Kiskiminitas and Pittsburgh stated that they contained "large and never failing springs, Coal in abundance, and a great deal of Fine Timber."3 In 1830 there were said to have been 24 salt wells in this county producing 327,000 bushels of salt, chiefly on the Kiski and Allegheny Rivers. In 1837 there were a number of wells in the vicinity of Freeport. As all the salt works on the Conemaugh River, were using coal long before 1830,4 it is safe to say that a considerable tonnage of coal was used for some years in these plants. In 1837 a tract of land in Clarion Township having a new saw mill and abounding "in Stone Coal" was offered for sale,5 and also one in Toby Township having "an abundance of the best quality of iron ore and stone coal."' In 1839 an advertisement in the Pittsburgh Mercury said

Jan 1, 1942

By Edward Schuster, Frank Feuille

As the time allotted is short, we can present only a general idea of the oil laws in the Latin-American republics, as a supplement to Bulletin 206 of the Department of the Interior compiled under the direction of J. W. Thompson of the Bureau of Mines and entitled "Petroleum Laws of All America." We shall not discuss the European colonies in Latin-America nor the island republics. As to the countries discussed, we shall attempt to give the main features of such special petroleum legislation as has been adopted prior to the early part of this year; where no special petroleum laws exist, we must look to the mining codes for light on the petroleum policy. As the laws and regulations for the extraction of the metals are often difficult of application to, and are lacking in many essentials for, the petroleum industry, it is best for persons or companies desiring to enter, on a large scale, into the petroleum exploration and development of countries not having special petroleum legislation, to obtain a concession contract from the executive of the country under consideration, and to have the concession approved by the congress. If this concession, which would then be a special law, contains nothing contrary to the constitution of that country and does not infringe on vested rights of third parties, it should be reasonably safe. If in such country there is some doubt as to whether the petroleum subsoil is owned by the nation or the private surface owner, only public lands should be covered with the concession. Guatemala is the only republic in the group that discriminates directly against foreigners. Bolivia, Ecuador, Mexico and Venezuela require waivers of diplomatic protection.' Colombia requires foreigners to agree to be bound by its alien law. In addition,Mexico makes it unlawful for foreigners to acquire direct ownership of real estate, including mines, within a zone of 50 km. along the coasts and one of 100 km. alongitsland

Jan 1, 1923

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-' in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.' The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964

By J. J. Becker

BEAN1 has discussed the magnetic behavior of mixtures of small ferromagnetic particles on the order of 20 to l000A in diam. As he points out, there are three size categories with characteristic properties: 1) Particles large enough to contain many ferromagnetic domains magnetize initially by the motion of domain walls. The initial susceptibility of such particles, if domain-wall motion is assumed to be perfectly easy, depends only on their shape. It is equal to the reciprocal of the demagnetizing factor (and is thus 3/4 tt for a sphere) and is independent of temperature. 2) Smaller particles find it energetically undesirable to contain domain boundaries. They are always spontaneously saturated, and reverse their magnetization only by rotation of their entire magnetic moment. As assemblage of such particles has a remanence which is a large fraction of the saturation of the assemblage; its coercive force is on the order of 2K/1,, where K indicates magnetic aniso-tropy from any source, and I, is the saturation magnetization of the substance of which the particles are made. 3) Particles which are still smaller continue to be single-domain, but the direction of their magnetization fluctuates thermally, as first pointed out by Neel.' They have no remanence and no coercive force and possess the temperature-dependent magnetization curve of a paramagnetic substance with a very large moment. Bean calls this superpara-magnetism. All of these kinds of behavior are observable in alloys consisting of a precipitate of ferromagnetic phase in a nonferromagnetic matrix. Fig. 1 shows a typical aging curve for the room temperature coercive force of a sample of 98 pct Cu-2 pct Co alloy

Jan 1, 1958

By R. Grierson, L. J. Bonis

The high-temperature Strength oF TD nickel has been observed to be dependent upon the previons thermal and mechanical history of the material. Variations in both the level and the anisotropy of strength have been observed. 01 this paper- these variations are correlated with the storing of annealing resistant elastic strain energy in the matrix of the TD nickel. An x-vay line -broadening tecknique is used to measure the maLrTis elastie strain. THE inclusion of a finely dispersed second phase into a ductile matrix has long been recognized as an extremely effective method of strengthening the matrix both at high and at low homologous temperatures. It has been found, however, that the factors which determine the high-temperature strength are not the same as those which are important at low temperatures. Below 0.5 Tm the size and distribution of the second phase particles are of prime importance in determining the strength,')' while above this temperature the strength is mainly dependent upon the previous thermal and mechanical history of the alloy,3-7 This paper is primarily concerned with explaining the response of the high-temperature mechanical strength of one of these alloys (DuPont's TD nickel) to various thermo-mechanical treatments. It will be shown that this response is not associated with the occurrence of any form of dislocation substructure within the matrix of the alloy. It has been found, however, that a correlation does exist between the elastic strain level in the matrix and the previous thermomechanical history of the alloy and that the observed changes in elastic strain level parallel the measured changes in high-temperature strength. It therefore must be concluded that variations in high-temperature strength are a direct result of the variations in elastic strain level. MATERIAL TD nickel contains approximately 2 vol pct of Tho2 in an unalloyed nickel matrix. It is formed, as a powder, by a chemical technique and this powder is compacted to form ingots which are then extruded to give 21/2-in.-diam rod. Rod of smaller diameter is prepared from the as-extruded rod by swaging. In the studies reported in this paper, 1/2-in.-diam rod was used. This rod received an anneal of 1 hr at 1100°C prior to being used in any of these studies. EXPERIMENTAL TECHNIQUES Two methods were used to examine the structure of the nickel matrix of the TD nickel. These were: 1) transmission electron microscopy; 2) the analysis of the position and profile of X-ray diffraction lines obtained using the nickel matrix as the diffracting media. To prepare thin foils for electron-microscopical examination, slices of TD nickel approximately 0.050 in. thick were cut from the as-received 1/2-in.-diam rod. These were then chemically polished down to 0.045 in., rolled to 0.009 in., given a predetermined heat treatment, and thinned, using a modified Bollman technique, to provide the foils for observation. All observations were carried out at 100 kv, using a Hitachi HU-11 electron microscope. Specimens of the undeformed rod were prepared by grinding down the 0.050-in.-thick slices to approximately 0.015 in. and then thinning chemically and electrolytically to give the thin foils. The X-ray specimens were prepared by rolling 0.375-in.-thick rectangular blocks down to 0.075 in. The surfaces of the rolled material were ground flat, chemically polished to remove the layer disturbed by the grinding, and given a predetermined anneal in an inert atmosphere. They were then ground lightly to check their flatness and given a final chemical polish prior to being examined. The X-ray diffraction line profiles were measured using an automated Picker biplane diffractometer. A special specimen holder was built to allow a more accurate and reproducible positioning of the specimen. The line profiles were determined by carrying out intensity measurements at intervals of either 1/30 deg or 1/60 deg over a range of 3 deg on either side of the nickel peaks of interest. A piece of pure nickel which had been recrystallized to give a large grain size was used as a standard to give the X-ray line profile generated by a strain-free matrix. The analysis of the X-ray diffraction line profiles is a modification of that due initially to Warren and Aver-bach8and has been described elsewhere.3 This analysis gives a measurement of two parameters associated with the structure of the nickel matrix. These parameters are: 1) the size of the coherently diffracting domains within the nickel matrix; 2) the magnitude of the elastic strains in these domains. Both of these parameters are first determined in terms of a Fourier series. These series are obtained from other Fourier series which describe the measured profile of the X-ray diffraction lines. Thus, for both the coherently diffracting domain size and the elastic strain level, it is possible to plot Ft (the Fourier coefficient) against t (the term in the Fourier series), where t can be expressed in terms of a distance L and the Fourier coefficient Ft(S) (associated with elastic strain level) can be expressed in terms of the root mean square strain (e2)1/2. Thus a plot of (F 2)1/2 vs L can be obtained. Plots of this type are shown graphically in Figs. 6 and 8. Interpretation

Jan 1, 1968

By V. H. Gottschalk

SEVERAL years ago a group in the metallurgical division of the U. S. Bureau of Mines began a study of the application of new developments in physics to metallurgical problems'. Among these developments were the extensions of what may be termed by analogy the "sound spectrum." Electromagnetic waves, from X-rays to radio waves, have been quite thoroughly explored for metallurgical use, but the sound spectrum, extending from low-frequency vibrations involved in certain types of metal failure by fatigue through the range of audible sound to inaudible vibrations having frequencies of many kilocycles, has had only meager consideration from metallurgists. Because of the general interest in the process recently demonstrated by St. Clair3 for flocculating smoke by means of sound waves, this article is written to point out possible applications of sound and supersonic (ultrasonic) waves in the metallurgical industry.

Jan 1, 1937

By D. de Fontaine

A convolution procedure is described for obtaining an analytical expression for the composition profiles of solute concentration:; in binary solid solutions. The free energy of solutions containing such compositional inhomogeneities can then be evaluated and the stability of spherically symmetric clusters (G.P. zones, for short) us a function of their radii and central compositions can be studied accordingly. Two characteristic zone radii are defined: the minimum radius (RM) corresponding to the smallest zone for which growth is energetically favored over dissolution, and the critical radius RK) corresponding to zones associated with the minimum work of formation. The values of RM and RK coincide at the two classical limits of nucleation and growth and spinodal decomposition. As the spinodal is approached, however, RM and RK diverge increasingly and it is proposed that the initial] decomposition morphology is governed more closely by the minimum, rather than by the critical radius since the former possesses no singularity within the m eta stable phase boundary. Reversion is briefly discussed in the light of the foregoing and it is shown that a set of reversion temperatures located between the coherent miscibility gap and the coherent spinodal must correspond to a given distribution of low temperature zones. SINCE the early works of Guinier1 and preston,2 the kinetics and morphology of GP zones have been studied extensively, see Ref. 3, for example, for a recent review. Nevertheless, a completely satisfying theoretical treatment of the decomposition of meta-stable or unstable binary solid solutions is still lacking due to the almost unsurmountable mathematical difficulties that one encounters in attempting to solve the pertinent diffusion equation which, in principle, describes the whole process. This equation, first derived by Cahn for the initial stages of spinodal decomposition,4 is a nonlinear partial differential equation of the fourth order in anisotropic space, a general analytical solution of which is completely out of the question. From this equation, some prediction can be made, however, concerning the later stages of spinodal decomposition5 and a recent numerical solution6 of the equation in the case of one- and two-dimensional composition modulations of a solid solution inside the spinodal has led to the following considerations: the sinusoidal morphology7 is to be expected only for solutions of average composition c, located near the center of the coherent miscibility gap.8 For solutions with co closer to the spinodal decomposition, depleted shell zones9 should constitute the first recognizable decomposition product, later evolving to iso- lated, enriched preprecipitates in a uniformly depleted matrix as this must, in all cases, constitute the final metastable morphology, barring, of course, loss of coherency and change in crystal structure. In agreement with the qualitative description of Bonfiglioli and Guinier,l0 it thus appears that the various models discussed by previous authors are, in fact, idealized successive stages of the general decomposition process. Unfortunately, corresponding calculations for a solid solution outside the spinodal are not yet available because of two additional difficulties: it is essential that the diffusion equation be solved in three-dimensional space, and furthermore, one must include in the equation an appropriate "source term" describing the statistics of the creation of composition fluctuations required to trigger the nucleation events. At present, a general treatment of this problem does not appear to be tractable. Nevertheless, by using a modelistic approach, i.e., by selecting a priori certain composition variation profiles and by evaluating their associated free energies, one can draw certain conclusions relative to the stability of these isolated composition modulations or "zones", both outside and inside the spinodal. This is the object of the present investigation. THEORY We shall now describe a standard four-parameter spherically symmetric GP zone, evaluate its free energy according to the Cahn and Hilliard11 formula (Eq. [5], below), and plot the corresponding energy surfaces as a function of zone amplitude and radius as

Jan 1, 1970

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By W. H. Somerton

The effects of drilling variable on rotary drilling rates and efficiencies have been studied by a series of laboratory drilling tests. TWO-cone 1.25-in. diameter hits were used to drill vertically upwards into rock samples at corltrolled weights and rates of rotation. Shale, sandstone and specially prepared concrete samples were used in this study. Power input to the ririllirig systeln was measured and drilling chips collected for energy — .size reduction studies. Reasouably good correlations between drilling variables and rates of penetrotion were found. Qrrantities that are difficult to evaluate include rock strength parameters and the effects of bit wear. Effects of bit size and geormetry require further investigation. Analysis of the drilling chips confirmed the premise that, for rocks containing two or more mineral constituents of diflerent strengths, a greater amourrt of rock breakage occurs in the weaker constituent. Drilling conditions which required greater amounts of energy produced finer drilling chips. As bit tooth wear progressed, drilling chips became finer. Efficiency of rotary drilling as a rock breakage mechanism was extremely low. Comparison was made with theoretical energy requirements and with energy requirements for size reduction by comminution methods. INTRODUCTION Many technological developments and innovations have made possible the successful drilling of oil wells by the rotary method to depths exceeding 20,000 ft. Bigger, more powerful rigs, better steels, improved bit design and more careful control of the circulating system have all contributed to this success. Despite these advances comparatively little is known regarding the basic mechanism of rock breakage by the rotary drilling process. Future improvements and, in particular, reduction of drilling costs will undoubtedly require a clearer understanding of the variables controlling effectiveness and efficiency of rotary drilling. Rotary drilling is inherently an inefficient means of producing rock breakage. Loss of energy in transmission from the surface to the cutting mechanism may be large, thus limiting the total amount of energy which may be applied to rock breakage. Increased efficiency may be realized by improved energy transmission methods such as the turbodrill. Conversion of transmitted energy to rock breakage by use of rotating cutter teeth is likewise inefficient. Improvement of cutter efficiency has been obtained essentially by empirical means —changes in bit tooth size, shape and spacing, and tooth deletion to give clean bottom-hole patterns. The present work was undertaken to investigate the factors controlling rates of bit penetration under laboratory drilling conditions. Laboratory drilling apparatus is shown in Fig. 1. The effects of rock strength and bit wear on drilling rates were investigated. Drill cuttings were analyzed to determine the character of breakage and to compare this with other methods of producing rock breakage. VARIABLES INVOLVED IN ROTARY DRILLING Some of the variables controlling bit penetration rates can be studied conveniently by dimensional grouping. R/DN f(F/D2S) or

With the exception of the mentions of coal in Illinois in the period 1660-1680, already referred to, the first coal found in the United States was in the James River, Virginia, field. In 1699 a large tract of .land above the present city of Richmond was allotted for a settlement of French Huguenots by the colonial, government, near the present Manakin, about fourteen miles above Richmond. They soon found coal, tradition says it was uncovered by a hunter pulling out a small tree in a. steel) bank near a stream, and Colonel William Byrd, F.R.S., the most prominent man of his day in the colony, wrote to the Colonial Council of Virginia, May 10 and 11, 1701: "The 10th of May, last., I with Coll. Randolph, Capt. Epes, Capt. Webb, &c., went up to the new settlements of ye French Refugees at ye Manaken Town.... We went tip to ye Cole, w'ch is not above a mile and a half from their settlement on the great upper Creeke, w'ch, riseing very high in great Raines hath washed away the Banks that the Coal lyes bare, otherwise it's very deep in the Earth, the land being very high, and near the surface is plenty of Slate.", Some of the Frenchmen were evidently familiar with the use of coal, as on May 22, 1702, "David Menestrier a black smith and one of ye french Refugees Inhabiting at Luciana Petitioning his Excellency that he may have leave to use ye coal mines lately discovered there for his forge his Excellency by and with ye advice of ye Council loth hereby give Leave to ye said David Menestrier to take what coales he shall want. out of ye said Coal mine for ye use of his forge according to ye Prayer of ye said Petition."2 There was some uncertainty about the grant of these lands to the Huguenots which caused the request for leave to use this coal, as a Virginia patent in its usual form allowed the owner to mine all minerals excepting gold and silver, which were subject to royalties for the Crown. After the visit to the coal above mentioned, "Wm. Byrd, understanding the land had not been granted to the French, took out a patent for 344 acres, including the same, (the coal) which patent was dated October 20, 1704".3

Jan 1, 1942