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By H. R. Peiffer, R. Geckle

The silver phase of silver and finely divided alumina composites is shown to grow as single crystabs upon solidification from the melt. These crystals grow without the aid of an externally applied thermal gradient or a mold. The single-crystal growth is more readily disrupted as the alumina content varies from the optimum concentration of 20 wt pct. Pretreatment such as variation of fabrication pressure, and presintering of the specimens appear to play a lesser role in this phenomenon. In actual practice the growth of single crystals of metals from the melt is a tedious, painstaking process.' Care must be taken to insure the proper thermal gradients and rate of growth in a vibration-free environment. Excellent single crystals can be grown when these variables are controlled. When a second insoluble and finely divided phase is present in the melt the growth of single crystals is difficult, if not impossible, even under the most favorable conditions outlined above. During the past few years, a composite of silver and alumina has demonstrated an ability to resist flow even though the major phase, silver, is mo1ten. 2 A more surprising feature of this material is the ease with which single crystals of silver grow upon cooling the composite from temperatures above the melting point of silver to temperatures near room temperature. Observations have been made that demonstrate that single crystals of silver will grow even when conditions most unfavorable for growth of pure silver crystals exist. The crystals grown in this manner are imperfect in that a great deal of subgrain structure exists. It is the purpose of this manuscript to qualitatively describe this process and to attempt to isolate the influencing factors of this behavior. MATERIAL PREPARATION The composite material is prepared by powder-metallurgical techniques. Two items of great importance are the introduction of oxygen into the system and the obvious need for a thorough mixing of the metallic and refractory oxide phases. The oxygen is necessary in order that the silver wets the alumina. Without oxygen the phases separate and the material shows no unusual properties. In order to supply the needed oxygen the silver is added in the form of silver oxide which is readily decomposed to oxygen and silver upon heating. The silver oxide is readily obtained in a finely divided form that allows a uniform mixture of the alumina and silver oxide to be prepared. The correct ratio of alumina to silver oxide is mixed in the presence of alcohol in an ordinary food blender. The mixture has the consistency of a thin slurry and after mixing for approximately 20 min is dried and pressed into billets at various pressures. As is shown in Fig. 1, there is no limit to the shape of the specimens obtainable as single crystals. These billets are heated in air in a predeter-

Jan 1, 1964

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

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

Jan 1, 1955

By G. K. Manning, A. R. Elsea, C. R. Simcoe

Boron increases the hardenability of hypoeutectoid steels by decreasing the nucleation rate of ferrite and bainite. It is postulated that concentrations of lattice imperfections, such as exist at the grain boundaries, furnish the necessary energy for nucleus formation. Boron, because of its atomic diameter, will concentrate at lattice imperfections where sites of suitable size are present. Boron will decrease the energy of these local areas by occupying these sites. This mechanism accounts for the large increase in hardenability observed with small amounts of boron. The loss of the boron hardenability effect and the boron precipitate formation are explained on the basis of increased concentration of boron at the grain boundaries either with increasing boron content of the material or with increasing temperature. COMMON alloying elements affect both the nucleation and growth rates of the austenite decomposition reactions.' This effect is largely a result of the slow diffusion rates of these elements. Although a small addition of boron markedly increases the hardenability of steel, the diffusion rate of boron, which is of the same order of magnitude as that of carbon, can hardly account for this effect. An addition of boron in the range of 0.001 to 0.003 pct is about as effective as an addition of 0.30 pct Mo, 0.40 pct Cr, or 1.25 pct Ni in increasing the hardenability of a 0.40 pct C steel;' however, increasing the carbon content of the steel decreases the effectiveness of the boron addition."' The difficulty in understanding why so small an addition of boron can replace much larger quantities of the more strategic alloys, together with the erratic behavior sometimes encountered in boron-treated steels, has interfered with their general acceptance by industry. In the belief that an understanding of the mechanism by which boron increases the hardenability of steel should lead to a more general acceptance of boron-treated steels, a research investigation to determine this mechanism was undertaken at Battelle Memorial Institute under sponsorship of Wright Air Development Center. Experimental Work In order to study the effect of boron on the transformation of austenite to ferrite and bainite, a group of steels was made with a basic composition similar to that of the SAE 8600 series. This base composition was chosen because it has sufficient hardenability to permit accurate measurement of the times required for transformation to start at various temperatures. The chemical analyses of the steels used in the first part of this investigation are listed in Table I. These steels were made as 200 lb heats in an induction furnace. The furnace charge was Armco ingot iron with the alloying elements added as ferroalloys. After the alloy additions were made, the heat was deoxidized with 0.125 pct Al. A 100 lb ingot was cast and an addition of 0.003 pct B, as ferroboron, was made to the metal remaining in the furnace. This metal was cast into a second 100 lb ingot. The ingots were forged to 11/4 in. diam bar stock from which end-quench hardenability specimens were obtained. Part of this material was further reduced by hot rolling to lx¼ in. bar stock from which specimens were obtained for isothermal transformation studies. Studies of Nucleation and Growth: End-quench hardenability tests were performed on these steels, using an austenitizing temperature of 1600°F. The hardenability curves, shown in Fig. 1, indicate that boron treatment resulted in considerable increase in hardenability of the steels. Any such change in hardenability must result from a change in the transformation rate of the austenite, and these rate changes can be established readily by isothermal transformation studies. Isothermal transformation studies were conducted on these steels as follows: specimens were austeni-tized at 1600°F for 15 min, transferred to a lead bath operating at a constant subcritical or intercritical temperature, held for various lengths of time, and water quenched. The specimens were sectioned for metallographic examination to determine the amount and the type of transformation products present. In order to determine the effect of boron on the formation rate of ferrite, isothermal transformation tests were made on the 0.20 pct C steel in both the boron-treated and boron-free condition at an intercritical temperature of 1375°F where ferrite is the only decomposition product of this low carbon austenite. The results of these tests are shown in Fig. 2, where the percentage of ferrite formed is plotted as a function of time at temperature. It is apparent that boron markedly decreased the transformation rate of austenite to ferrite at this temperature.

Jan 1, 1956

By H. E. Biber

DURING the production of tin plate a thin layer of FeSn2, is formed at the interface between the steel sheet and the protective tin coating. Because excessive amounts of this alloy layer are undesirable, the kinetics of its formation is a subject of interest in the tin-plate industry. A recent study of this subject at our laboratory uncovered a relationship which should be of general interest to anyone studying kinetics of reactions in metallic systems. It had been previously concluded that, at any given temperature in the range 175" to 330°C, the Fe-Sn alloy layer would have a parabolic growth rate.1,2 However, our studies showed that this rule apparently holds only when the tin plate is heated very slowly to the "reaction" temperature; when the tin plate is rapidly heated, considerably different growth rates occur. An example of this effect of heating rate on growth behavior is contained in the accompanying results of alloy-layer growth measurements at 240°C in oil baths stirred at 10,500, 1800, and 0 rpm. The heating curves for these three conditions are given in Fig. 1, and the growth data are presented in Fig. 2. With the rapid heating rate, provided by the stirring at 10,500 rpm, the alloy layer had three distinct stages of growth. In the initial stage, which persisted well beyond the time required to heat the tin plate to bath temperature, the alloy layer formed very rapidly. The growth followed a rate law of the form w = ktn where n > 1. This initial stage was followed by a growth-retardation stage of about 50-sec duration in which little additional alloy was formed. In the third stage the growth again followed a rate law of the form w = ktn, but here « =0.3. With the intermediate heating rate provided by stirring at 1800 rpm, the three-stage nature was less pronounced and the slope of the third stage increased (i.e., n > 0.3). With the slow heating rate provided by the unstirred oil bath, the alloy layer grew in two stages. The initial rapid-growth stage persisted only until the specimen was heated to bath temperature, no growth retardation was observed, and the slope of the main portion of the plotted data was greater than in the stirred baths, having a value of almost 0.5. Similar results were obtained for other bath temperatures in the range 200" to 300°C. This effect of heating rate on growth behavior may be due to changes in the rate of nucleation of FeSn, crystallites. The iron and tin are in contact from the onset of heating. Thus the initial formation of FeSn, occurs not at the "reaction" temperature but rather while the tin plate is being heated to that temperature. Because nucleation is in general temperature-dependent, different heating rates could cause different over-all nucleation rates, which in turn could cause different growth behaviors. A more detailed discussion of the growth of Fe-Sn alloy layer and the effect of heating rate will be published shortly.

Jan 1, 1965

By P. B. Liebermann

The haulage of coal from the face to the tipple is an important enough link in the production of coal to deserve its full share of study and care. In order to obtain a better understanding of mine haulage conditions, a series of tests and investigations has been made which promises to hasten the improvement of present conditions. For hauling coal through the mine and on the surface, locomotives are required, the size and power consumption of which depend on the resistance to motion offered by the mine cars. This resistance is principally caused by gravity and bearing friction. The effect of gravity can be reduced to a minimum by a suitable layout of the haulageways; that is, by arranging the grades in favor of the loaded trips, and by fixing the percentage of grade to that value which gives the lowest power consumption for loaded and empty trains. The bearing friction, which is considerably greater than is generally realized, can be easily reduced to a negligible quantity by the installation of a suitable anti-friction bearing that will stand the rough use and abuse of coal-mine service. The present investigation will deal with flexible roller bearings in comparison with ordinary plain bearings. A number of tests for determining train resistance have been run during the last 2 years both in the bituminous and anthracite coal regions. For all these tests the dynamometer car described in a previous paper was used. This car is equipped with recording instruments and is entirely automatic in its operation. It is coupled between the Iocomotive and train, and records the following quantities: drawbar pull in pounds, speed in miles per hour, and a time interval, usually 5 sec.; the paper travel is proportional to the distance covered by the car. Opposite these records the profile of the road is drawn in by hand so that full particulars

Jan 1, 1918

By I. R. Kramer

Single crystals of aluminum were pulled in tension in a solution of paraffin oil and stearic acid. The critical resolved shear stress did not change with the concentration of the stearic acid solution; however, the extents and slopes of Stages I and II were affected greatly. The observations lend evidence that the weakening effect of surface-active agents is controlled by the rate of desorption of the metal soap formed by the reaction of the surface-active agent and the metal surface. IT has been shown by various investigators1-" that surface-active agents markedly affect the mechanical properties of single crystals. (A surface-active agent, for the purpose of this report, is defined as a long-chain organic molecule which contains one or more polar groups. Usually, however, investigations have considered only molecules having one polar group.) In general, when single crystals are deformed in some solutions containing surface-active agents, the creep rate, Fig. 1, is increased and the yield strength is decreased. The fatigue strength has been reported to be affected also.ll Rehbinder and his asociatesl' explained the "weakening" effect of surface-active agents in terms of physical adsorption. They assumed that a large pressure was created in microcracks which existed on the surface of the crystal." Harper and Cottrell,' from their study of the effects of surface conditions, found that the deformation characteristics of zinc single crystals were not altered by a solution containing a surface-active agent unless the surface of the specimen had an oxidized surface. They concluded that the role of the polar molecule was to remove the strengthening effect of the oxide coating. Later, And-radeetBpresented additional evidence which appeared to agree with this conclusion. In contrast, Klinken-berg et al.7 reported data which confirmed the results of Rehbinder. Using zinc and cadmium crystals which had been cleaned by electrolytic polishing, a large increase in the creep rate was observed when Lle specimens were tested in a 1 pct oleic acid-paraffin oil solution. They also reported that the creep rate

Jan 1, 1962

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

As a result of using copper-containing scrap in the steelmaking process, the copper content of steels has been steadily increasing for years. Consequently the possible role copper may play in the steelmaking process and in the finished product begins to attract the metallurgists' attention. Some time ago one of the present authors forwarded the idea—based on the results of the analysis of nonmetallic inclusions extracted electrolytically from steels—that sulphur in plain carbon steels is distributed mainly between copper and manganese, the amount of iron sulphide being very small; and that, consequently, the problem of copper and that of sulphur in steel cannot be treated separately.' At the time of the publication of the quoted paper little was known about the relative affinities of copper and manganese for sulphur at high temperatures except that at moderate temperatures (below 1000°C) the affinity of manganese for sulphur is much greater. To gather more experimental data on this subject, the present authors undertook the investigation of the equilibrium constants of the reactions: 2Mn(8 or 1) + S2(g) = 2MnS(s) 4Cu(s or 1) + S2(g) = 2Cu2S (S or I)* 2Fe(s) + S2(g) = 2FeS (s or 1) over a range of temperatures wide enough to establish the dependence of these equilibrium constants on temperature. From the equilibrium constants (K = l/Ps2) the free energy of formation (affinity) can be calculated from F° = -RTln 1/PSt (1) where the standard conditions chosen are: 1 atm of sulphur pressure and the activities of condensed components equal one. The decomposition pressure, Ps2, of sulphur over the respective sulphides is too small to be measured directly, but there is a way of eliminating this difficulty by measuring the equilibrium constant of the reaction between the sulphide and hydrogen. From the latter and from the equilibrium constant of the thermal dissociation of H2S we then calculate Ps2 for the respective sulphide. 2Mn + 2H2S = 2MnS + 2H, 2H2 + S2 = 2H2S_________ 2Mn + S2 = 2MnS The numerical values of the equilibrium constant of the thermal dissociation of H2S at different temperatures were taken from Kelley's paper, "The Thermodynamic Properties of Sulfur and its Inorganic Compounds."² In previous experimental work published by Jellinek and Zakowski3 and by Britzke and Kapustinsky4 the equilibrium constants of the reactions Metal sulphide + H2 = H2S + metal were determined by passing hydrogen, at different rates of flow, over the sulphide, analyzing the resulting H2S + H2 mixture and then extrapolating the H2S/H2 ratio (which is a function of the rate of flow) to the zero speed of flow, a method necessarily involving considerable uncertainty. In the present work the equilibrium ratio was actually measured instead of being extrapolated. The apparatus is shown in Fig 1. Experimental Procedure The sulphides were prepared by the following methods: FeS Powdered iron which had been reduced with hydrogen (ferrum reduc-tum) was mixed in stoichiometric ratio with sublimed sulphur and carefully ground. The mixture was put into an alundum crucible, covered with pure sulphur, and the reaction started by touching the mixture with a glowing iron rod. After the reaction was completed the product (still containing some metallic iron) was again ground with sulphur, put into a Rose crucible, covered with sulphur, and heated in a strong current of pure hydrogen. Analysis of the final product showed 62.46 pct Fe and 36.59 pct S. Theoretical for FeS: 63.53 pct Fe and 36.47 pct S. MnS Manganese sulphide (precipitated and carefully washed with distilled water containing H2S) was dried in a Rose crucible in an atmosphere of H2S and heated in a current of hydrogen for 2 hr at red heat. The product was then ground and ignited for several hours at 1000°C in a current of hydrogen sulphide. Analysis showed 64.53 pct Mn and 36.63 pct S. Theoretical: 63.15 pct Mn and 36.85 pct S. Some MnS samples were prepared from metallic manganese and sublimed sulphur by mixing and grinding them and then heating in a current of hydrogen sulphide in an alundum tube.

Jan 1, 1950

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,' but neglected one2' which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By R. D. Pehlke, J. V. Gluck

The effect of small additions of silver on the actiziity of zinc in dilute solution with molten bismuth has been determined ill the range 450° to 650°C. Experimental measurements were made in a multi-electrode galvanic cell. All zinc activities showed large positive deviations from Raoult's Law. The results are expressed in terms of the interaction parameter EJ, as defined by Wagner. In the binary Zn-Bi system, Henry's Law was followed at zinc concentrations below 5 mol pct, thus indicating that the binary or self-interaction parameter of zinc in bismuth is essentially zero. The Henry's Law con- THE determination of thermodynamic interaction parameters requires accurate knowledge of solute activities in the dilute-solution region. Dealy and Pehlke1 have summarized the basis for interaction relations, discussed some theoretical implications, and presented a compilation of interaction parameters calculated for molten nonferrous alloys from stant ranged from 2.43 at 650°C to 3.96 at 450°C. The binary zinc activities were consistent with published data for higher zinc concentrations . The ternary interaction parameter ranged from -1.90 at 650°C to -3.30 at 450° C, varying linearly with the reciprocal of the absolute temperature. The negative value for the parameter reflects the fact that addition of silver decreases the activity of zinc in solution with bismuth. data available in the literature. Most of the data were for two-component systems from which only the self-interactions, Ei, could be calculated. Concentration ranges were often such that a considerable extrapolation was required for calculations at lnfinite dilution. The data for ternary systems were quite limited and often unavailable in suitable systematic fashion—thus few values of the parameter e| could be obtained. Knowledge of both the binary and ternary interaction parameters is necessary for the estimation of the activity coefficient of a given dilute solute in

Jan 1, 1965

By Willard S. Morse

The purpose of this paper is to record the results obtained in the use of the Russell process at Aspen, Colo., covering a period of fourteen months, from November, 1891, to December, 1892, during which time over 30,000 tons of ore, purchased outright, on sample and assay, were treated. No explanation of results will be attempted, nor will the chemistry of the process be discussed. The plant was designed by C. A. Stetefeldt, of San Francisco, and built by the owners by day-labor. The entire plant is run by water-power, supplied by a flume 3600 feet long, and a pipe-line 2200 feet long, with a head of 170 feet. A Pelton water-wheel, 8 feet in diameter, is used, from which power is transmitted by wire-rope to the main counter-shaft in the mill, a distance of about 250 feet. From the mill to the samplingworks, about 150 feet, power is also transmitted by a wirerope. A Pelton water-wheel, 3 feet in diameter, supplies power to the dynamo for lighting the plant. The works are located adjoining the Santa Fe railroad tracks, and all ore and supplies are unloaded directly from the cars to the works. The sampling-works are provided with crushers and rolls, the latter being used only on samples, and not on the entire ore. The Cornish hand-quartering method is used in sampling ore for purchase. After crushing and sampling, the ore goes to the bedding-floor, where it is made up into mixtures suitable for the mill. The drying-plant consists of four Stetefeldt double shelfdryers, six shelves high, and is provided with dust-chambers and a stack 65 feet high for draft. These dryers are fired with gas

Jan 1, 1896

By R. H. Thurston

THE writer became convinced, many years ago, that the generally accepted values of the coefficient of friction for lubricated surfaces were not applicable to such heavy machinery as he had been called upon, in the course of professional work, to design, to construct, and to operate. Experience frequently seemed to indicate, also, a wide departure, in such cases, from the accepted "laws of friction." In the year 1869, or earlier, he invented an apparatus to redetermine these laws and these coefficients for a wide range of temperatures, pressures and velocities. The construction of the machine was delayed, however, some time, and no experiments were made for several years, when, finally, the construction of the apparatus was commenced in the workshops of the Stevens Institute of Technology, and experiments were begun in the Mechanical Laboratory organized by the writer in connection with the Department of Engineering. These machines have now been in use about five years, and have furnished an immense amount of valuable information. Those now in use are of two styles: one designed and built by the Class of 1877, Figs. 1 and 2; the other a much larger machine, Figs. 3 and 4. The first has been already frequently described,* and a working drawing of the second has been also published.† For convenience, engravings of both are herewith reproduced. In the “'77 machine,” a journal, F, is made on the overhung extremity of a shaft carried in the two bearings, B B'. This journal is grasped by brass boxes which are carried in a pendulum, II H. They are forced against the journal by a screw which compresses a coiled spring with a pressure which is read off on the scale, N H. A weight at the lower end of the arm, at I, gives it the necessary resistance to deflection. The angle of deflection is measured on the * In Scientific American, Railroad Gazette, Jour. Frank. Inst., Johnson's Cyclopaedia, Knight's Mechanical Dictionary, etc. † Railroad Gazette, Jan. 18th, 1878, p. 25.

Jan 1, 1879

By C. W. Washburne

Continued discussion of the paper Of ROSWELL H. JOHNSON, presented at the New York meeting, February, 1015, and printed in Bulletin No. 98, February; 1915, pp. 221 to 226. See also Bulletin No. 101, May, 1915, pp. 1157 to 1162, and No. 103, July, 1915, pp. 1449 to 1450. C. W. WASHBURNE, New York, N. Y. (communication to the Secretary*).-Mr. Johnson recognizes that connate waters must be driven, outward toward the earth's surface. He considers the ascent due to the settling and packing of the underlying sediments and to the formation of gas within the rocks, supplemented by abyssal pressures. The origin of the methane in the sedimentary strata probably is not simple. There are three possible modes of origin: (1) as marsh gas formed near the surface and entrapped in the sediments; (2) from abyssal sources; (3) by the decomposition of organic matter buried in the sediments. The abyssal source is generally negligible, and in all cases doubtful. The third origin is the most important in the gas fields. A fourth mode of origin, by the dissociation of liquid hydrocarbons, frequently has been suggested, but it is improbable, because crude oils are exothermic. Therefore they have no tendency, to split or decompose at low temperatures, as do endothermic substances, such as coal, which is geologically by the loss of methane, water, and carbon dioxide. This cannot happen to a hydrocarbon until its temperature of dissociation (" cracking point") is reached, which is over 250'.C. for the most easily cracked hydrocarbons and over 400° C. for others. Engler says that the dissociation of fats and waxes into oils is an endothermic process, thereby unconsciously nullifying his own theory of the dissociation of these substances at low temperatures. However, recently I have found reason to think that heat is liberated by the disruption of the molecules of fats and waxes, as it is in the molecular decomposition of the substances of wood, coal, etc. If this tentative opinion is correct, and Engler wrong, then it seems that the Engler-Höfer hypothesis of the origin of oil becomes not only possible, but even probable.

Jan 9, 1915

By Roswell H. Johnson

What becomes of the water which must have filled the oil and gas sands at the time of deposition, has long puzzled students of oil and gas and has found expression in Munn's well-known article on the hydraulic theory. Both Munn and Clapp have pointed out that in the Appalachian field the deeper sands carry increasingly less proportionate amounts of water. It seems to me probable that the principal source of oil and gas has been in the shales in proximity to the sands which now contain these products. The sand spits which mark off the lagoons from the sea comply particularly with the requirements of a limited sand imbedded in shales rich in organic matter. Cunningham Craig has objected to this view that the rich organic muds of lagoons are found only at the surface. That such muds do extend to considerable depth 1 am assured by Prof. Douglas W. Johnson, who has made an extensive study of the Atlantic Coast marshes. As any particular sand body becomes weighted by a heavier and heavier overburden, the result of increasing deposition, a part of the very large percentage of water in the uncompacted sand and mud is forced out. The water percentage of freshly settled mud is vastly higher than that of the resultant shales, or even of a very porous sand. If beds of less compressible material meet or underlie the shales in question, there will frequently be a lateral motion along such beds to some point where the upward movement will be resumed. We find in our laboratory work here that oil, gas, and water have extremely slight capacity for gravitational sorting while in a state of rest, but when moving the gravitational sorting is readily accomplished. As the oil, gas, and water pass a body of larger pores, the gas, owing to its lack of capillary attraction, is retained in the large pores. This has been predicted by Washburne, Blatehley and others on the ground that the water has a higher capillarity and grips the finer pores in such a way that there will be a greater proportion of oil and gas in the large

Jan 1, 1915

By S. A. Lever, R. Hultgren

The solidus is usually the least satisfactorily determined portion of a phase diagram. Cooling curves, which succeed well with the liquidus, show the solidus inaccurately or not at all because of segregation which occurs during freezing. Heating curves of carefully homogenized alloys might be expected to indicate accurately the solidus, but they are seldom used. Dynamic methods involving heating or cooling are never completely satisfactory because of uncertainty as to whether equilibrium is attained. A static method in which the specimen may be allowed hours, days, or even weeks to attain equilibrium is to be preferred. In a static method a solid solution, for example, is first made thoroughly homogeneous, then heated to successively higher temperatures. After sufficient time at each temperature to assure equilibrium, some property is measured which should alter strikingly when melting begins. Microscopic examination can be used to detect the beginning of melting, but the method is tedious since the specimen must be quenched, sectioned, polished, and etched before each examination. Of all the physical properties which change on melting, electrical resistance is probably the most satisfactory to measure. The measurement may be made while the specimen is at temperature without damage to the specimen. It may be repeated indefinitely to ascertain when equilibrium has been achieved. Measurements may be made on a single specimen over the whole range of temperature. Most metals approximately double their resistance on melting. Since an accuracy of a few tenths of a percent is easy to achieve, the method is highly sensitive to the beginning of melting. In spite of these advantages, which have been perceived for a long time,l,2 a reasonable search of the literature has failed to reveal a single case in which the method has been satisfactorily applied in practice to the determination of solidus temperatures. The use of electrical resistance measurements appears to have been confined in practice to changes in the solid state. In the work described in the following pages we have applied the electrical resistance method to the solidus of the lead-tin system. We have found the method to be convenient, reproducible, and highly sensitive. We chose the lead-tin system because it leads to few technical difficulties. Furthermore, a number of determinations of solidus have been made in this system by various methods and results could be checked against them. However, all published results are not in good agreement with one another, so this work should help in determining the solidus more precisely. The Lead-tin Diagram Because of its commercial importance, there have been numerous investigations of the lead-tin diagram. The results of the most recent work on the solidus are indicated in Fig 7, as well as the results of the present work. The works of Honda and Abe3 and of Stockdale4 agree fairly well with each other and with the present work. Jeffery's5 data indicate the solidus to be about 50°C lower. Honda and Abe3 used differential thermal analysis on both heating and cooling cycles. Stockdale4 used the microscopic method and also differential heating curves. Stockdale's results were about 4" higher than those of Honda and Abe at low tin contents and lower at higher tin contents. These results also agree with those of Rosen-hain and Tucker.= Jeffery5 used electrical resistance measurements of the alloy as it was being heated or cooled. Apparently he did not attain equilibrium as his results are about 40°C lower than those of Stockdale4 or Honda and Abe.3 MATERIALS AND METHODS The lead and tin used were of high purity. They were supplied by the American Smelting and Refining Co., who gave the following analyses: Lead: silver, 0.0016 oz per ton; copper, 0.0008 pct; cadmium, 0.0007 pct; zinc, 0.0002 pct; arsenic, 0.0003 pct; antimony, 0.0002 pct; bismuth, 0.0005 pct; tin, 0.0001 pct; iron, 0.0020 pct; lead (by difference), 99.995 pct. Tin: antimony, 0.037 pct; arsenic, 0.020 pct; bismuth, 0.004 pct; cadmium, trace; copper, 0.025 pct; iron, 0.004 pct; lead, 0.020 pct; nickel and cobalt, 0.005 pct; silver, 0.0005 pct; sulphur, 0.005 pct; tin (by .-difference). 99.88 pct. One hundred grams of metal with the desired proportions of lead and tin was weighed out to the nearest one-tenth of a milligram. The mixture was placed in a silica crucible, covered with charcoal, and melted in a reducing atmosphere in a gas-fired furnace. The alloy was well stirred. Chemical analysis of two of the alloys checked closely with the weighed portions. The compositions of the remainder of the alloys were taken directly from the weighings, without chemical analysis.

Jan 1, 1950

By Robert T. Hill

The successful completion, January 10,1901, by Capt. A. F. Lucas, of a well, near Beaumont, Texas, whereby an enormous flow, estimated at '75,000 barrels a day, was obtained, opened a new oil-field in the United States, kindled a frenzy of exploitation and speculation, revolutionized the fuel industry of a large region, and brought gain to thousands of people. Even to-day, it is impossible to cast up the present results or to prognosticate the future influence of this event. It has caused the revival of attention in other localities where oil had been suspected, and exploration for oil throughout the Texas region. It has attracted notice to the mineral resources of the Texas region, and created an interest in the geological conditions of that great State. This State, which has increased in population and wealth, as recorded by every succeeding census, with leaps and bounds such as are exhibited by no other part of the Union, now stands fifth in population and first in productive wealth per capita. Its fields, pastures, forests and mines teem with raw material. The whole economic evolution of the State has gravitated toward a focal point where these products were available for the coming of the kiln, the machine and the factory. The only drawback to the prosperity of the State was the lack of an economic fuel, inferior coal costing an average of $5.00 per ton at the time of the Beaumont discovery. This

Jan 1, 1903

By James Douglas

I had the good fortune to visit the Stockholm Exposition just before its close in October last, and to get a glimpse of the methods used in Sweden in making the wonderful steel and iron for which its furnaces are so famous. My time and opportunities for observation were limited, but some points which I noted may be worth bringing to the notice of the Institute. The Exposition itself was confined to the natural and artificial products of Scanclinavia, and therefore iron and steel held a very prominent place in it. There was a complete collection of the rocks and ores of the Peninsula made by the Geological Survey; and every iron-mine of note exhibited a glass model of its workings, as well as classified specimens, accompaniecl by thorough analyses of the ores. Another feature of interest was the display of models of the old mining-machinery, in the invention and introduction of which Sweden led the way, and of the old and new surveying-instruments and compasses devised for the exploration of the Swedish iron-ore bodies, all of which are more or less magnetic. The magnetometric collection and exhibit of methods of operation made by Prof. Nordestrijm were supremely instructive. The larger metallurgical works, such as those of the Kopparberg and Sandvik companies, exhibited their wares in separate pavilions, in which crude and manufactured objects were arranged most eflectively and tastefully; while the smaller companies erected in the Industrial Arts Building trophies, every one of which was an object of beauty. One was struck on all sides by the fine asthetic feeling exhibited in the ingenious installation of materials and objects not easily lending themselves to artistic treatment. Hammers, picks and drill-steel were grouped into mural designs which it was a delight to look at.

Jan 1, 1899

By C. G. McLachlan

This paper outlines a series of tests carried out during the first six months of 1927, in the laboratory and mill of the Moctezuma Copper Co. The object of the tests was to determine whether the soluble salts present in the mill circuit water were having a detrimental cffect on the recovery made by flotation. To accomplish this object a series of water analyses were made, followed by flotation experiments in which definite quantities of the salts found were added as addition agents. Before proceeding to describe the results obtained in the course of the investigation, reference will be made to five articles that have appeared during the last two years in which the action of such salts is discussed. Two of these are by A. T. Tye1, 2 and describe flotation practice at Cananea and the way in which water high in ferrous and ferric salts is conditioned for differential flotation. Two, one by A. C. Munro and H. A. Pearse3 and the other by H. A. Pearse,4 outline Britannia milling methods, and the advantages that have been derived from ore washing; while in the fifth, A. W. Hahn5 summarizes the results of laboratory experiments in which ferrous, ferric and aluminum sulfates have been added in varying amounts. The mill of the Moctezuma Copper Co. has a daily capacity of 3000 tons, and is situated about 75 miles south of Douglas, Arizona, on the Rio de Nacozari, in the Mexican state of Sonora. The ore treated is mined from the company's mine at Pilares, about 5 miles southeast of the Concentrator. This ore contains about 2.5 per cent. copper— present almost entirely as chalcopyrite—and 10 per cent. iron, of which

Jan 1, 1928

By G. R. Kotler, W. A. Tiller, W. C. Johnston

Experiments carried out on 100 g samples of molten tin and Sn-Pb alloys showed that the magnitude of the field strength, H, does not effect the supercooling, aTn, at which the initial nucleus of solid forms. However, the nuwlber of nuclei forming per cc, n, is found to increase greatly with H for fixed ATN and to increase with ATN for fixed H. The value of n increases greatly with the presence of solute and is found to he indefiendent of the cooling rate of the simples. Further, the most effective time for stirring to enhance n is immediately following the initiation of recalescence. The effect of inducing nucleation with the aid of a mechanical impact both in the presence and absence of stirring has also been studied. All proposed mechanisms for the enhancement of n by physical means seem to be inadequate in accounting for these results. IN any real nucleation experiment there are two effects influencing the results that would not be predieted from classical homogeneous nucleation theory. These may be separated into chemical and mechanical effects. The chemical effects are twofold. 1) Nucleation catalysts are present which enhance the nucleation frequency of new grains over that predicted by classical homogeneous nucleation theory.' 2) Solute will restrain the growth of nuclei so that many others may form.2,3 The mechanical effects are also two-fold. 1) Vibration (sonic or ultrasonic) of the freezing liquid enhances the nucleation frequency of new grains over that given by the chemical effects alone.4-6 2) Macroscopic fluid-flow effects produce the same effect as l).'7' It is also possible to influence the nucleation experiment by certain physical effects such as the application of electric and magnetic fields.9 From classical homogeneous nucleation theory one would predict the following relationship between the nucleation rate, N1 (number of nuclei formed per unit volume per unit time), and bath supercooling, AT, for an isothermal experiment.

Jan 1, 1963

By R. M. Rose, K. A. Jones

Resistive measurements ulere made on superconducting niobium single crystals in transverse magnetic fields. Crystals were grouln in both high and ulfrahigh vacua, doped with stnall quantities of oxygen, and annealed in ultrahigh vacua at temperatures from 900' to 1350°C. Maxima in the fluxoid pinr~ir~g force were observedfor the [100] and [210] directions. The increase of the critical current density with dissoved oxygen was seen to saturate at relatively low concentration. This behavior, and the variation of J, and residual resistivity (as a function of oxygen content and annealing) of both clean and dirty gassy) crystals, is seen as a consequence of the formation of clusters with (210)~b habit planes and (200)ffo common boundaries. These suboxide clusters are apparenlly stable at high temperatures and very low oxygen concentrations. It is generally known that dissolved oxygen at concentrations well below the solubility limit sharply increases the critical current density of superconducting niobium.' Such a result would not be expected if Nb-0 solutions were random, not even as the result of segregation on the scale usually encountered in solid solutions. According to the Kim-Anderson theory of flux creep,' the critical transport current density is determined by the pinning force Fp associated with some feature of the microstructure. As the Lorentz force. a or (J X R), of the transport current in the magnetic field approaches Fp, flux creep and then flux flow occur. The pinning force is expected to be quite small if the heterogeneity involved is significantly smaller than tte range of coherency which for niobium is circa 250~.~ Although the strain field of an individual oxygen atom in the niobium lattice is relatively large, it does not seem plausible that individual atoms could be so effective as to account for the data. Also, ~ramer~ found that straining and strain aging specimens containing small amounts of oxygen on occasion decreased the residual resistivity. A possible explanation for the above behavior may be found in the work of van Ooijen and van der Goot,= who found that annealing changed J, for niobium foils containing oxygen, and they attributed the changes to ordering of the oxygen atoms. This phenomenon has been observed by other investigators using X-ray and PROCEDURE Cylindrical 4-in.-diam niobium single crystals with axial orientations [ill], [110], [112], and [oo~] were grown from pure niobium, see Table I for analysis, in an ion-pumped ultrahigh-vacuum system using the electron beam floating zone technique. Total pressure during growth was lo-'9 torr: the oxygen partial pressure was less than lo-" torr, as determined by a mass spectrometer. These crystals will be referred to as the "clean" crystals. Similar crystals were also grown in another system at a pressure of 5 X 10"6 torr. These crystals will be referred to as the "dirty" crystals. Specimens 14 in. long were cut from the as-grown crystals and one end was polished down to no. 600 carbide paper smoothness. A back-reflection Laue photograph was then taken in order to fix the crystallo-graphic directions transverse to the crystal. The critical current density J,, the current density necessary to produce a voltage drop of 1.0 pv between voltage leads placed a in. apart, was determined as a function of the magnitude and direction of the transverse magnetic field and of the oxygen concentration. The technique and experimental arrangement was essentially similar to that of Tedmon et al.' In the remainder of this paper, the azjmuthal angle $ for the field H is referenced to the [ I101 direction in all four crystals, and oxygen was added in small equal increments by anodization and annealing.7 The resistivity ratio, RR, of the resistance at room ternperature to that at 4.2"K (H =7.00 kG) was determined as well.

Jan 1, 1970

For a nation whose mining industry has generally been floating through history in the shadows of major mining developments elsewhere in the world, Australia has in the decade of the Sixties made a convincing bid to be one of the world's great "store- houses" of minerals. In fact, at the rate things are developing Down Under and Out Back, what with professional prospecting teams crisscrossing the continent under the direction of professional exploration management, Australia may one day find itself as the world's greatest storehouse. Whereas Necessity may be the Mother of Invention, Consumption is surely the Mother of Exploration. At least this is true in Australia of today. First, the forecasted shortage of iron ore in the world led to the fabulous discoveries in the Pilbara district of Western Australia. Now, the demand for nickel has generated even more interest among mining companies in the vast, untapped potential of Australia.

Jan 10, 1968