Search Documents

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By M. M. Austin

Pure metallic tantalum, from a practical standpoint, is one of the newer developments in the metal field. Although it was used as filament in incandescent lamps in 1906, only within the last, five years has the metal been available in sufficient quantity and suitable form for more general application. In addition to corrosion-resisting properties and high melting point, the metal has an ability to withstand unusual amounts of cold working. It affords some striking demonstrations of block movement during plastic flow. Strength and Ductility of Tantalum Since there is no good way of defining working properties numerically, illustrations will be used. It is possible to roll a bar of pure tantalum 0.4 in. thick to sheet 0.001 in. thick, without heating or annealing. The sheet produced will be sound and may be bent upon itself at right angles to the direction of rolling. Longitudinally the sheet will be somewhat brittle. A disk of annealed metal may be cupped and drawn to the form of a capsule 3/16 in. dia. by 146 1? in. long. If carefully handled this capsule can be further deformed by drawing to a tube having an outside diameter of 0.050 in. Disks of tantalum may be spun into tubes of 39 in. dia. and 1½ in. long. In the form of rod, reductions may be made from 0.4 in. to 0.001 dia. In the latter process, it is necessary to heat the wire four or five times to 500" C., at intervals between 0.040 and 0.001 in. Although the melting point of tantalum is 2850" C., these heatings at 500" C. are sufficient to distinctly anneal it. Published figures on the strength and ductility of tantalum are not particularly accurate. This is due to the fact that these properties vary widely, depending on the extent to which the metal is contaminated by gas. There are no sharp critical points in these changes with gas content; samples of metal will vary from a springy or actually brittle condition to one of leadlike softness. Samples that have had a prolonged heating at high temperatures in a good vacuum, under conditions such as would be provided in vacuum-tube experimentation, will yield a product of about the hardness of annealed copper. The usual commercial metal will have the hardness of annealed mild steel.

Jan 1, 1930

By T. M. Geffen, R. E. Gladfelter

Lipson1 has recently presented a technical note wherein theoretical considerations were used to demonstrate. that the adsorption us saturation relation for a linear absorption method is not necessarily a single valued function of saturation.1 It was concluded that the absorption us saturation relationship is subject to the same hysteretic effect as is the flow behavior between the drainage and imbibition systems. It is the purpose of this note to show, by experimental results, that for the manner in which fluids are distributed in porous materials during fluid flow, the relative X-ray absorption us saturation relationship is single-valued regardless of the saturation history. The design of the apparatus used to measure relative X-ray absorption of cores undergoing fluid flow tests is similar to that described by Morgan, McDowell and Doty. A few modifications have been incorporated in the design to increase sensitivity and simplicity of measurement. The sensitivity is such that for usual types of cores a recording pen movement of approximately 12 linear in. is occasioned between the recording of the core dry and when it is completely full of an absorbing liquid, a solution of approximately five per cent by volume of iodo-benzene in a close-cut hydrocarbon fraction, or a solution of 50,000 ppm sodium iodide in water. Two types of experiments were conducted, one in which the liquid was inside the core, and the other with the liquid outside the core. Tests with the liquid inside the core were run to cover the saturation range encountered in both the drainage (gas drive) and imbibition (liquid flood) flow systems. It is pointed out that the same core was used, but the tests were conducted at different times with the recording mechanism balanced at a different position. Therefore, the absolute values of relative X-ray intensity at any saturation are not the same in each test. In the second type of test the same core was used, but this time its pore space cmtained only gas, and various thicknesses of oil contained in plastic cells were placed in front of the dry core. As before. the relative X-ray ah- sorption was measured and compared to the quantity of oil in front of the core. The arrangement of the fluids with respect to the path of X-rays in these two types of tests represent fluid distributions of a wider difference than can be expected between that established in a core just due to imbibition and drainage saturation flow histories. Thus any deviation from a straight line relationship of the log of the relative X-ray intensity us saturation calibration should be readily apparent. Results of the laboratory tests are given in Fig. 1. A schematic diagram showing the position of the fluids with respect to the path of the X-ray beam is given for the two cases investigated. In the case where the oil existed outside the core (Case B), the log of the X-ray intensity (log, I/I,) is related directly to the cell thickness (amount of oil in X-ray beam path). This correlation is in full agreement with X-ray theory. In the case where the oil or water existed inside the core (Case A) which covers both drainage and imbibition types of flow processes, again the relationship between absorption and saturation (amount of oil in X-ray beam path

Jan 1, 1952

By Alex Hay

THE Sydney coal field, the largest and most valuable in Nova Scotia, is situated on the northeastern coast of the Island of Cape Breton, extending from Mira Bay on the south to Cape Dauphin on the north, a distance of 30 miles, and has a general dip northeast under the sea. (Fig. 1.) The field embraces the mining villages of Morien, Birchgrove and Reserve and the towns of Dominion, Glace Bay, Waterford and Sydney Mines. The city of Sydney is situated about midway between the northern and southern extremities of the field and on the western fringe of the productive coal measures. Sydney harbor crosses the coal field, cutting off direct rail connection between Sydney Mines and the greater part of the field to the southeast. (Fig. 2.) The coal measures are exposed in the cliffs on the coast line, which rise to an average height of 30 ft., and are almost continuous throughout the length of the field. The portion of the coal field under land forms a small segment of a circle, the greatest distance from the coast landwards is 9 miles, and it occupies an area of 200 sq. miles. The greatest distance developed seawards from the shore by mining operations is 2 ¼ miles. The strata maintain a regularity of dip at this distance, proving a submarine area of about 70 sq. miles. How much further the coal field extends seawards is unknown, but the indications are that it extends far beyond the present economical working limit and in all probability there is a vast submarine coal field. The productive coal measures are of Carboniferous age, these being underlaid by beds of sandstone, locally classed as millstone grit, which define the southern limit of the field,, while a spur of syenitic hills cuts off the coal-bearing strata on the north. Two main anticlinal folds having a general course easterly divide the field into three basins named from north to south: Sydney Mines-Lingan, Glace Bay and Morien.

Jan 1, 1929

By Edgar S. Cook

Portions of this paper repeat in substance the statements made by me in an address before the meeting of the American Society for Testing Materials, held in June, 1903, at Delaware Water Gap, Pa. The views I then expressed, I still hold and believe to be pertinent to the present discussion of this subject. In doing my part, therefore, at the request of our Secretary, towards the further consideration by the Institute of the Physics of Cast-lron from a commercial as well as a theoretical standpoint,—a theme which received interesting treatment in our meeting some years ago, but has been somewhat neglected recently,—I make no apology for reiterating the views I have expressed elsewhere. Indications all point to the substitution of classifying pig-iron by chemical analysis for the old-time method of grading by fracture. Commencing with the larger users, and the makers of specialties, who require more positive information as to the composition than is afforded by the fracture; the use of pig-iron, guided by analysis, has spread with much greater rapidity to all classes of foundry-work than the most sanguine expected. Grading by fracture, as guided by experience with any particular brand of iron, has some points in its favor. The fact that, for so many years, castings of multitudinous forms, and for an endless variety of uses, were made in a fairly satisfactory

Jan 1, 1905

By Albert Phillips

As EARLY As 1824, Haidinger1 described crystals of native copper that were, according to Dana,2 "probably twinned parallel to the octahedral plane and normal to this axis." In 1837, Rose3 very clearly demonstrated that native copper crystals were commonly twinned on the octahedral plane. Lasaulx,4 in 1882, described polysynthetic octahedral twins and stated that enclosed twinning lamellae were observed. Even on crystals formed artificially by. electrolysis, twinning was observed as early as 1886, by Brown.5 Many other descriptions of twinning in native copper and in gold and silver are to be found in the literature, and in every case with which we are acquainted the twinning is conformable to the spinel law; i. e., the octahedral plane is both twinning and composition plane. Metallurgists have long been familiar with the straight-sided bars or bands that commonly occur within the irregularly outlined grains of metallic crystalline aggregates. They are certainly found in nearly all metals of the face-centered cubic type after cold working and annealing. If a specimen showing these bands is rotated, keeping the angle of incidence of the illuminating beam constant, they usually exchange color contrast periodically with their respective matrix crystals. Also slip lines, when produced in these specimens, nearly always show a change in direction upon passing through the bands, giving rise to the "stairway" effect often illustrated in metallurgical textbooks. Apparently the only quantitative observations on bands of this sort were made by Osmond and Cartaud6 on austenitic steel. They selected,

Jan 1, 1928

By Ernest Gayford

This is a nontechnical paper on flotation, subdivided under three general headings: (I) Definition of flotation; (2) what flotation is now doing in Utah; and (3) what is the future of flotation? Definition T. A. Rickard defines flotation' as "the act or state of floating," from the French flottaison, water-line and flotter, to float. The dictionary defines flotation as "the science of floating bodies." The flotation process is a method of concentrating ores by frothing. Weinig and Palmer,2 define flotation as follows: What is the flotation process? Briefly, it consists in the agitation of finely divided ore in water containing bubbles of air or gas, a small amount of oil and, usually, other reagents, soluble and insoluble; under these conditions the small particles of native metals, sulfides, arsenides, antimonides, selenides and tellurides show a tendency to attach themselves to the films of the bubbles, and are thus carried to the surface of the water. The oxidized gangue minerals, such as quartz, feldspar, limestone, hematite, etc., show much less affinity for the bubbles, are easily wetted by the water, and either remain in suspension in the water, or sink to the bottom of the vessel. If the bubbles are sufficiently stable they can be removed, carrying their load of sulfide-mineral particles with them. Thus there can be effected a separation of the two classes of minerals from each other, assuming that the grinding has been sufficient to unlock all of the particles of different composition. The separation does not depend upon differences in specific gravity of the various minerals; in fact, the sulfides are usually heavier than the oxides, and some of the heaviest sulfide minerals are the easiest to float. A particle of mineral may be so large, however, that its weight will counteract its affinity for the film of the bubble. In most cases the ore must be fine enough to pass a screen having at least 48 meshes to the linear inch. Taggart3 defines flotation as follows: Flotation is a method of wet concentration of ores in which separation of mineral from gangue is effected by causing the mineral to float at or above the surface of a body of liquid pulp while the gangue becomes or remains submerged. The method

Jan 1, 1928

By AIME AIME

APPARENTLY unperturbed by any misgiving as to ill luck connected with the mystic number thirteen -for there were exactly that number of Directors on deck-the Board held two sessions on Tuesday, Feb. 21. , . Between the executive session at 5:15 p. m. and the general session at 8:30 p. m., 28 Section and Division delegates were wests of the Directors at dinner. Committee chair- " men and past officers brought the attendance to 75. Messrs. McAuliffe, Merica, Mudd and Tally had expressed their intention to be at the Directors' meeting, but each was prevented unavoidably at the last minute. At the executive session of the Board, J. V. W. Reynders was unanimously chosen to fill the unexpired term of Dr. Becket as Director: and Eugene McAuliffe in like " manner was selected to become Vice-president to fill the vacancy created hy Dr. Becket's assumption of the Presidency. Upon nomination of President Becket the following Executive Committee was appointed: Frederick M. Becket, chairman; Howard N. Eavenson, H. A. Guess, J. V. W. Reynders and William Wraith; and the Finance Committee was appointed as follows: Henry Krumb, chairman; Paul D. Merica and H. G. Moulton. Karl Eilers was reelected Treasurer and A. B. Parsons was re- elected Secretary to serve for the ensuing year, whereupon the executive session was adjourned.

Jan 1, 1933

By J. M. Dahl, R. J. Warrick, O. K. Riegger, H. Van Vlack

A liquid which is rich in oxygen (and silicon) develops at steel rolling temperatures in resulfurized and plain-carbon steels. This liquid fluxes solid manganese sulfide. The composition of the liquid and the resulting microstructures vary with the manganese/silicon/oxygen ratios in the steel. The observations and conclusions zuhich are presented are used 1) to suggest a mechanism for MnS deformation in resulfurized steels, and 2) to rationulize hot-shortness anomalies between plain-carbon and resulfurized steels. 1 HIS is a summary of the dependence of sulfide inclusion microstructures upon steel composition, and an interpretation of the behavior of sulfide inclusions at steel-rolling temperatures. Sulfide inclusions are known to have several metallurgical effects upon steel. Their effects upon hot-shortness are best appreciated. Although hot-shortness is well known, it is questionable whether its mechanism is fully understood because there are several anomalies in our interpretation. For example, why should not high sulfur contents produce extensive hot-shortness in free-machining steels ? A second metallurgical consequence of sulfide inclusions appears because sulfide inclusions improve machinability. Furthermore, globular inclu- sions are to be desired over elongated inclusions. To date, we know that lower silicon contents (< 0.010 pct) favor the globular sulfides, but we do not know why this interrelationship between silicon content and inclusion shape exists. Finally, the evidence is strong that the surface quality of a hot-rolled steel is particularly sensitive to the sulfur content. SUMMARY OF PREVIOUS WORK The role of sulfur in hot-shortness was first suggested during the past century. It is uncertain who was the first to conclude that sulfur was less deleterious in the presence of manganese, and that manganese altered the sulfide phase from a liquid FeS to a solid MnS at steel-rolling temperatures. However, Urban and chipman&apos; emphasized that liquid FeS may accumulate as an interdendritic film during solidification. More recently, Keh and Van lack&apos; showed that the intergranular liquid does not completely surround the metal grains at all rolling temperatures. Rather, a small finite dihedral angle exists when geometric equilibration is attained at

Jan 1, 1962

By David Turnbull

IN isothermal recrystallization processes, new crystals generally grow into the matrix until they impinge upon other new crystals or an external surface, at constant linear rates G. Before impingement the perceptible course of growth can be described by the equation: 1 = G(t-7) C1I where, G = dl/dt, 1 is a crystal dimension measured in a constant direction, t is the time, and 7, the nucleation period, is a positive intercept on the time axis. Fig. 1 is a schematic representation of I as a function of time for a recrystallizing grain. G is dependent upon temperature, driving energy (strain or surface energy), relative grain and boundary orientations, but is generally independent of time. The frequency of nucleation, fi, (time" volume") can be defined by the equation: N = 1/fV [2] where ? is the mean nucleation period and V is the volume of the specimen that has not recrystallized. The kinetics of primary and secondary recrystallization generally can be described satisfactorily in terms of the parameters N and G only.&apos;-" After recrystallization is complete the average grain size 7 increases with time by "normal grain growth;" didt, the average rate of grain growth, is strongly time dependent and has not yet been precisely related to G for the motion of the individual grain boundaries constituting the system. It has been suggested4* " that the elementary act in grain boundary migration is closely related to the elementary act in grain boundary self-diffusion. Although the distance of atom movement in the two processes may be somewhat different, there is reason to expect that the activated states may be very similar, so that the free energy of activation for grain boundary migration should be of the same order of magnitude as for grain boundary self-diffusion. Therefore, it is desirable to develop a satisfactory basis for comparing data on self-diffusion and grain boundary migration and to make such comparisons where possible. Theory The formal theory of grain boundary migration rates is analogous to the theory for the rate of growth of crystals into supercooled liquids reviewed elsewhere 6-8. Boreliuss has shown that the latter theory describes, within the theoretical uncertainty, the growth of selenium crystals into supercooled liquid selenium. Motto and more recently Smolu-chowski" have derived expressions for the rate of boundary migration in recrystallization. The treatment to be presented is similar to Mott&apos;s excepting that the formalism of the absolute reaction rate theory will be used. The atomic mobility, M, in grain boundary migration is defined by: G = -M6p/6x where p is the chemical potential per atom and x is the coordinate measured in the direction of grain boundary movement. Let AF be the free energy difference per gram atom on the two sides of the boundary and k the thickness of the boundary. For RT>>AF the potential gradient across the boundary (6p/6x) is essentially linear and it follows that: SF/8x = - aF/N\ [4] where N is Avogadro&apos;s number. According to the Nernst-Einstein equation, M is related to a diffusion coefficient, Do, for matter transport in grain boundary migration by the equation: M = Da/kT [5] Substituting eqs 4 and 5 into eq 3 gives the basic relation between Do and G: G = DoaF/\RT [6] Do values may be calculated from experimental values of G from eq 6 and directly compared with the coefficient of self-diffusion within the crystal, DL, or the grain boundary self-diffusion coefficient D,. However, a more convenient, though equivalent, basis for comparing atomic mobility in grain boundary migration and self-diffusion is through the constants of the absolute reaction rate theory. According to this theory diffusion coefficients may be written:" D = k2(kT/h) exp [-AF,/RT] 171 aFa, the free energy of activation, is related to the measured energy of activation, Q, by the equation: AFA = Q - T aSx - RT [8] where aSa is the entropy of activation. Substituting eqs 8 and 7 into eq 6 gives: G = ek(kT/h) (aF/RT) exp [(AS,,)C/R] exp C-Qc/RTI C91 where the subscript G refers to boundary migration. The relationship between the driving free energy and the free energy of activation in boundary migration is indicated schematically in Fig. 2. Experience indicates that the variation of G with temperature can be described by: G= Go exp [- Qc/RT] [10] where Go and Qc are generally temperature independent over wide ranges of temperature. Comparison of eq 9 with eq 10 gives:

Jan 1, 1952

By M. T. McDonough

THE data relative to the effect of metal depth on slag volume was obtained from the operation on two acid electric furnaces in which heats of various sizes were produced. The furnaces used were of 3 and 5-ton rated capacity; the heats investigated ranged from 6 to 8 tons. Heats of 7 and 8 tons were made in the larger furnace; heats of 6 tons in the smaller one. Bath depths and diameters were measured on the furnaces when cold and each is accurate to one inch. Both the metal charge and the slag were weighed on a track scale accurate to ± 25 lb. All other components added to the furnace were weighed on a wheelbarrow scale accurate to ±5 lb.

Jan 1, 1947

By Milo W. Krejci

(Butte Meeting, August, 1913.) THE plant and quarries of the Inland d Portland Cement Co.. are located- at Metaline Falls, Wash, about 128 miles north of Spokane, on the Fend Oreille river, and 10 miles, of the Canadian border. The plant is one of a chain of cement plants controlled by the Lehigh Portland Cement Co., of Allentown, Pa. Work on this plant was commenced in June, 1910, and was completed in April, 1911, but on account of some delays in the construction of the power plant, the works were not put into operation until August., 1911. Since then it has been in continuous operation and has furnished the Inland Empire with a high grade of cement. Fig. 1 is a, view and Fig. 2 is a plan of the works. Water Power Development.-The source of the water supply for the hydro-electric plant of the Inland Portland Cement Co. is Sullivan lake, a body of water approximately 5.5 miles long and 0.5 mile wide, situated in the Kanisku Forest Reserve. A wooden crib dam was installed so as to raise the elevation of the lake 25 f and the additional storage capacity was taken up by the diversion of Sullivan creek into the lake by means of a wooden flume, 0.25 mile long, 6 by 8 ft. in crosssection, and a ditch 1,200 ft. long. The water from the lake follows the natural water course to an intermediate storage reservoir, which was created by the construction of an earthen dam. This pond was used in connection with the saw mill which was installed at this point. Besides the earth dam, there was also built a crib, at the point shown in the sketch map, Fig. 3. This crib dam is 35 ft. high. From this point the excess water follows the natural -course of Sullivan creek to the Pend Oreille river.

Jan 7, 1913

By A. T. Shurick

THE present economic crisis in bituminous coal is substantially the most insidious, and critical, in the modern history of the industry. The large consumption deficit that has gradually developed (almost unawares), has culminated in a situation that has forced home the urgent necessity for prompt and radical remedial measures, such as the various mergers now in course of negotiation. Conditions today are sufficiently comparable with those in the iron and steel industry, preceding the formation of the United States Steel Corpn., to suggest the possibility of a sweeping super-consolidation, that all but staggers the imagination. The important function of the banker in this, and lesser projects, is too well known to require comment, and it is important that we understand clearly just what these functions are. Certain features in banking practice came up for consideration in connection with a rather exhaustive economic study into the prospective future of the coal industry, upon which I was recently engaged for an Eastern bituminous interest. This survey was made for the purpose of effecting a decision on certain pressing questions of policy, involving considerable capital expenditures, that would be compatible with the flattening out in the curve of production in recent years. An examination of the TRANSACTIONS, and the coal literature generally, failed to disclose any pertinent, and authoritative data, on this subject. This was more or less characteristic of the whole survey, which had involved a large amount of original research, and measures were taken to procure the required information. The following notes have been compiled largely from the data thus collected, supplemented with material, suggestions and criticisms, by several of the larger banking houses active in coal, together with personal memoranda of my own.

Jan 1, 1928

By Edward Sampson, Allan B. Griggs

SURVEYING of many holes drilled by the U. S. Bureau of Mines in the Metaline district has shown surprising deviations. The holes start in the Ledbetter slate (Ordovician) and pass into the underlying gently dipping Metaline limestone (Cambrian) at varying depths, locally in excess of 1000 ft. All holes start vertical, but one had deflected as much as 35° at a depth of only 300 ft. One hole was found to be deflected 70° at a depth of 1000 ft. These deviations were not indicated to the drillers by any action of the rods or machines. Analysis of the survey data in the light of the observed geology indicates that the holes deviate most in the Ledbetter slate and scarcely at all in the Metaline limestone. The upper part of the "limestone"&apos; in most holes is a massive rock strongly altered by hydrothermal action and essentially homogeneous. The slate is only obscurely bedded but has a cleavage, varying from slight to strong, which is unrelated to bedding. Drill holes have deflected to become nearly perpendicular to the cleavage. Several plans and cross sections are submitted showing the behavior of various holes.

Jan 1, 1946

By C. W. Washburne

Recently, Messrs, Mills and Wells1 published a thorough chemical study of the waters associated with oil in parts of the Pennsylvania, Ohio, and West Virginia region. Many of their conclusions are of general application and the writer wishes to discuss some of these. Messrs. Mills and Wells show that the composition of the deep brines oi the Appalachian fields is such as would be produced by the evaporation of sea water and the precipitation of sodium chloride, combined with reactions with hydrocarbons and other substances. The brines are altered, also, by considerable mixing with meteoric water. They give good reasons for believing that the concentration of the brines was produced by evaporation in the rock pores induced by migrating gas, much of which probably escaped to the surface of the ground. This hypothesis was considered by the writer in a former paperJ2 in which main stress was laid on a second hypothesis, that the excess of chlorine in the deep brines may have been due to the entrance of solutions rich in magnesium and calcium chloride which ascended from a deep, possibly intratellurie, source. Messrs. Mills and Wells present good arguments for the first hypothesis. Underground evaporation by ascending gases probably will be accepted as the best available explanation of the concentration and composition of deep well waters. They have not considered the possibility that salt waters in deep sands may be concentrated by the diffusion of water vapor through gas into shale. The writer has given reasons3 for believing that capillary forces concentrate gas and oil in the larger openings of rock, such as the pores of sandstones embedded in shale. The gas underground must be nearly saturated with water vapor at all times, because it always is in contact with the interstitial water of enclosing shales and of the sandstone. Experimental studies of soil moisture have shown that approxi-

Jan 1, 1921

By James T. B. Ives

The map exhibited* as an example of my method of construct ing geological strata-maps is essentially an educational appliance. The method, however, is available for the production of maps of comparatively small areas, which, I am confident, will be found of great practical value to mining engineers. Before stating how the method may be so applied I will briefly describe the map exhibited, as the easiest way of making my meaning clear. Almost any region might be taken. This map represents the eastern half of the United States; and the geology is that of the map issued by the Geological Survey, and revised and extended subsequently by Professor Hitchcock for your Institute. I use ten cards, of the colors used in the geological map, each having the geog raphy of the area printed upon it; and I superimpose these in the order in which the colors occur in the index to the map. I next cut away a portion of each card, excepting the lowest, leaving only so much of each as represents the exposure of the formation of that color plus all those which overlie it. When that is done, the whole, looked at from a distance, appears to be an ordinary geological map. Looked at more closely, however, the formations are seen to overlie one another, as in nature. The cards are covered with glass in a frame, which, hinged at the bottom edge, can be let down. The cards are then found to be all hinged in the same manner, and they, too, may be lowered, one after the-other. I am told by teachers of geology of great experience and the highest reputation that by this appliance they will be assisted in im parting to students the first facts and principles of geological sci ence. Having let down the whole series of cards, until that repre senting the Archaean is seen underlying all the rest, the teacher will gradually rebuild it. The Cambrian will thus be laid down upon the Archaean before the eyes of the class, the Silurian upon that,

Jan 1, 1888

By N. S. Stoloff, M. Gensamer

Pyramidal (1122) slip was observed in cadmium single crystals deformed in compression and bending at room temperature and —196°C. Crystals tested in tension twinned with no evidence of pyramidal slip. A critical resolved shear stress law for the propagation of twin nuclei appears probable. Twinning and low-stress kinking are believed to inhibit the appearance of pyramidal slip under ordinary experimental conditions. SEVERAL reports of nonbasal slip in cadmium have appeared in the literature recently, two of the reports having appeared after work on this project was in progress. Brown1 reported cross slip on electron micrographs, but did not identify the cross-slip plane. Wernick and Thomas2 observed nonbasal slip traces parallel to [1123] on a crystal bent with a pair of tweezers, but this too was an isolated observation, with no confirmation of the glide plane. The critical stress for pyramidal glide, and the temperature and strain rate dependence of glide on this system were not discussed. price3 has reported some observations of nonbasal slip in thin films of cadmium with the aid of transmission electron microscopy, but a full publication of these observations was not available at this writing. Pyramidal (1122) <1123> slip also has been observed on zinc single crystals4, 5 and (1122) <1010> slip on magnesium single crystals,6 all oriented with the basal plane nearly parallel to the specimen axis. Since the choice of slip system in the hexa- gonal metals is generally believed to depend on the axial ratio, with basal slip predominating for high-axial ratios, the occurrence of pyramidal slip in zinc and cadmium is unexpected. The objectives of the present investigation were to confirm the existence of nonbasal slip in cadmium, to identify the slip system, and to obtain an estimate of the critical resolved shear stress, assuming that the resolved shear stress law is applicable. EXPERIMENTAL PROCEDURE Two purities of cadmium, 99.95 pet and 99.99+ pet, were employed. As received bars were cold swaged to 3/16 in. rounds. Bicrystals and tricrystals were prepared by passing the polycrystalline rods through a gradient without seeds. It was desired to obtain a large yield of single crystals oriented xo* < 5 deg, in order to be able to suppress basal slip during deformation by keeping the resolved shear stress on the basal plane to a minimum. Cylindrical single crystals of cadmium were prepared by a seeding technique developed by Weiner,7 to obtain a predetermined orientation. The single-crystal rods were sectioned to specimen size by an acid-cutting technique originally developed for zinc crystals.&apos; An aqueous solution of nitric acid was the cutting agent. The acid was picked up by a plexiglass disc spinning at an optimum cutting speed through the acid, which was contained in a sump-like arrangement. The section to be cut, the acid bath, and the spinning disc were enclosed in a plexiglass case. The rod to be sectioned was coated with a thick layer of collodion. At the points at which sectioning was to be effected, the collodion was removed over a length of about 1/8 in. by dissolving it in acetone. To prepare a surface suitable for microscopic exam-

Jan 1, 1962

By A. Vignes, J. P. Sabatier

A study of ternary diffusion at 1315°C in the Fe-Co-Ni system covering the entire ternary phase diagram has been carried out. Experimental values of the four interdiffusion coefficients DFeNico,DFeCoCo, DFeCoNi were computed at 33 points of the ternary diagram. The limiting values of these coefficients on the three sides of the ternary diizgram have also been determined. This set of data is presented as a contour map on the ternary isotherm for each of the four coefficients. Assuming that the Fe-Co-Ni system can be considered as ideal, the phenomenological coefficients Lk ij (with k = Fe) have been computed and the Onsager reciprocal relutions verified. It is shown that, in the Fe-Co-Ni system, the diffusion process can also be described by only two interdiffusion coefficients DFeFe and DCoNiFe, the second cross diffusion coefficient DCoFeNi being equal to zero and the second direct difusion coefficient being given by The values of the cross interdiffusion coefficients and of the Onsager coefficients are explained in terms of atomic mobilities of the three components with the help of a kinetic calculation due to Lane and Kirkaldy.8 It is shown that all the results are explained if the tracer difusion coefficients of the three components are such that DFe > DNi ~ DCo in complete agreement with experimental data on the three binary systems. DIFFUSION in a ternary alloy system is basically and significantly different from diffusion in binary alloys. In binary diffusion, there is just one independent composition variable and only one coefficient Dij is needed to describe the interdiffusion process. In ternary diffusion, we must allow for cross interaction between two independent species, and four interdiffusion coefficients are necessary to describe the transport process. Kirkaldy et al.1,2 have determined interdiffusion coefficients in the systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy4 have reported intrinsic diffusion coefficients for the r phase at 1300°C of Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.3 Interdiffusion coefficients were measured at three different compositions at 850°C in the single phase copper-rich corner of the Cu-Zn-Mn system by Dayananda and race.5 Zie-bold and Ogilvie6 have determined interdiffusion coefficients in the single-phase field of the Cu-Ag-Au system at 725°C. Preliminary results on diffusion at 1136°C in the system Fe-Co-Ni have been reported.7 In this study, data are reported on a more complete determination of interdiffusion coefficients in the Fe-Co-Ni system in the entire ternary at 1315°C. There is complete solid solubility with the fcc structures at 1315ºC, and this system can be considered as nearly ideal. This approximation allows the computation of the Onsager phenomenological coefficients. These values can then be used to test a kinetic calculation of the Onsager L coefficients in ternary substitutional solid solutions due to Lane and Kirkaldy.8

Jan 1, 1970

By B. Post, D. Moskowitz, F. W. Glaser

Lattice parameters of various hafnium compounds, two borides, a carbide and a nitride were determined. Some physical properties were measured and comparisons with the properties of the corre-sponing zirconium compounds were drawn. A LTHOUGH borides of transition metals have A been extensively investigated in recent years, there are few references in the literature to borides of hafnium. This is not surprising, in view of the extreme scarcity and great cost of the purified metal. Becker&apos; reported the existence of a boride, carbide, and nitride of hafnium; he listed the formulas as HfB, HfC, and HfN. However, in his work no mention was made of chemical analyses of the reaction products. In this paper results of a study of various hafnium compounds, including borides, carbides, and nitrides, are reported. It was expected, of course, that these compounds would closely resemble their zirconium analogues, which have previously been extensively investigated. Three borides of zirconium are known: ZrB,² ZrB,² and ZrB212.4 In addition, one carbide, ZrC,5 and one nitride, ZrN,5 have been reported. It should be noted that ZrB and ZrB12 are stable phases only in relatively high-temperature regions, unlike ZrB2, which is stable from room temperature to its melting point." It was felt that hafnium would yield corresponding borides, carbides, and nitrides with similar stability ranges. Experimental Procedures and Results A quantity of hafnium metal that was better than 97 pct pure, with zirconium as its major impurity, was furnished by the Argonne National Laboratories. The boron powder used was approximately 96.5 pct pure. In general, the procedure involved mixing the metal and boron powders in the desired proportions, and subsequently hot pressing them. The resulting specimens were analyzed chemically and phases present were identified by X-ray diffraction methods. A Philips Norelco Geiger counter spectrometer was used for identification of components and for measurement of lattice constants. Filtered copper radiation was used for all X-ray work. Electrical resistivity and density measurements were carried out at room temperature. The stable diboride, HfB2, will be described first. Stoichiometric quantities of boron and metal were heated to approximately 2000°C during hot pressing. The reaction product was shown by X-ray diffraction methods to be isomorphous with ZrB2 (space group Dlgh; P6/mm). Values of lattice constants of HfB2 compared with those of ZrB2 are shown in Table I. The calculated density of HfB2 is 11.2 g per cc, compared with a measured (pycnometric) value of 10.5 g per cc. HfB2 specimens prepared under a wide variety of conditions (including variations in initial Hf-B ratios) showed only insignificant variations in lattice constants, indicating a very narrow range of homogeneity. Like ZrB2,7 HfB2 is an excellent electrical conductor. The resistivity at room temperature of hot-pressed samples, approximately 85 pct dense, is 12 microhm-cm. This compares favorably with the electrical resistivity of 10 mi-

Jan 1, 1954

By J. S. Osoba, J. W. Graham, P. H. Monaghan

Of the many factors which affect the productivity of hydraudically fractured wells, the wettability of the propping sand has received little attention in the pas/. This paper shows that the wettability of the propping sand is an important factor which shorcltl not he overlooked. An analysis of relative permeability data shows that fractures packed with water-wet sand should be more permeable to oil than are fracturer packed with oil-wet sand. Laboratory results verify this conclusion. Cnlculations show that higher permeability to oil in the fracture should provide higher well productivity. A method is presented which ensures that the propping sand in an induced fracture is water-we1 even though oil is used as the fracturing fluid. The rnethod has been used in more than 150 field jobs: the field resrrlts are discussed briefly. The fluidized nature of water-wet sand in oil has giver1 unexpected benefits. This characteristic of water-wet sand and how it has been used advantageously in field operations are discussed. INTRODUCTION Hydraulic fracturing of subsurface strata to increase the productivity of oil and gas wells has been practiced for about 10 years. Today, fracturing is used more often than any other method of well stimulation. Basically, the process consists of breaking down (fracturing) a subsurface formation with pressure applied by means of a carrier fluid, usually oil or water, and propping the induced fractures apart by means of an agent, usually sand. suspended in the carrier fluid. Currently about 68 per cent of all fracturing is done with a simple mixture of refined oil or lease crude oil and sand&apos;. The research of other investigators has suggested that dry sand is rendered oil-wet when it is contracted with certain types of crude or refined oils.&apos; Hence, it may be expected that some fracturing operations employing an oil as the carrier for sand leave fractures packed with oil-wet sand. Conversely, those operations which employ water as the carrier for the sand probably leave the fractures packed with water-wet sand. Since the permeability of a sand-packed fracture to a mixture of oil and water is dependent upon the wettability of the fracturing (frac) sand, research was undertaken to determine to what extent the wettability condition (water-wet or oil-wet) controls fracture permeability which, in turn, affects well productivity. Additional research was directed toward the development of a method for obtaining the desired fracture wettability. In this report both theoretical and experimental evidence is presented to show the desirability of employing water-wet sand in fracturing operations. A method to obtain water-wet sand is discussed, and field results are reviewed briefly. DEPENDENCE OF WELL PRODUCTIVITY ON FRACTURE WETTABILITY To determine the dependence of well productivity on the wettability of the frac sand, it is necessary to know, first, the effect of fracture wettability on fracture permeability and, second, the effect of fracture permeability on well productivity. The relationship of these variables is considered separately in the order indicated. Effect of Wettability on Permeability Fig. 1 shows relative permeability relations for 20-30 mesh Ottawa sand. Inspection of these curves reveals that the relative permeability to oil when a small amount of water accompanies the flow is considerably higher when water rather than oil is the wetting phase. For