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By R. A. Bloom, John Birtalan

CONSIDERABLE interest has been shown in recent years toward determining the crystal structure, mode of formation, and chemical composition of the x phase, designated as such by Andrews,' who was the first to establish its presence in Fe-Cr- Ni-Mo alloys . Later work2 by the same author has shown that the occurrence of x depends on the presence of some molybdenum in the alloy. The phase, which appears to be identical or very similar to a manganese, has a body-centered-cubic structure and is closely related to s phase. Koh observed a similarity in composition between x and s and speculated as to whether x might be an ordered structure of u which is known to have a tetragonal crystal

Jan 1, 1957

By F. von Gemmingen, E. J. Fasiska, L. Zwell

EARLIER studies of the dependence of creep on structure1 and of the dependence of creep rupture on creep behavior2 did not include detailed discussion of the phases present in the specimens under examination. It is of interest to determine the nature and amounts of such phases present since it is well known that these are dependent on composition, heat treatment and creep conditions.3 This investigation has therefore been undertaken to identify these constituents and to determine their relative amounts. This report presents the results of this investigation and describes an improved "extraction replica" technique developed in the course of the work. The composition of the Type 316 austenitic stainless steels studied in this investigation is given in Table I. The specimens were solution treated at 2000°F for 1/2 hr and water quenched. Those specimens subjected to prestrain at room temperature Methods for extracting precipitate particles from materials for electron and X-ray diffraction analysis have been described by Fisher,4 Smith and Nutting: and Booker and coworkers.6'7 Electrolytic extraction methods have been described by Andrews and Hughes.8 The first two methods have been used at this Laboratory, but have not proved satisfactory for many problems requiring X-ray diffraction analysis. It has been difficult to remove the replicas or to avoid tearing them during removal. These difficulties are overcome by backing the replica with a water-soluble plastic such as Dupont 51-05 Elvanol (polyvinyl alcohol). The backing increases the thickness of the replica so that it can be mechanically stripped from unloosened particles without folding or tearing. This procedure eliminates the stripping of wet replicas, which usually have a low tear strength. By stripping replicas after drying, it is possible to extract partially loosened particles which otherwise would remain imbedded in the metal. The modified method is as follows: after the specimen is polished, it is etched for 60 min in modified glyceregia consisting of 30 ml glycerol, 7 ml nitric acid, and 4 ml of hydrochloric acid. The sample is then washed, air dried, and coated with a 20 pct Baker and Adamson 1611 collodion (85 pct amyl acetate by volume) film. After the collodion film is dry (about 15 min), the sample is again etched in the modified glyceregia for 50 min, washed with isopropyl alcohol (to prevent dissolving the collodion) and air dried. A very thick coat of polyvinyl alcohol (about 50 pct solution "Elvanol Dupont 51-05" in water) is poured over the sample and is permitted to dry for about 24 hr. The composite film containing the precipitates is then stripped from the specimen and floated, polyvinyl alcohol side down, in water (at about 50°C) until the polyvinyl alcohol dissolves. This usually takes about 15 min. Should any of the polyvinyl alcohol remain on the replica, it does not give a crystalline diffraction pattern and therefore does not hinder identification of the precipitates. The extraction replica, floating in water, is picked up on a glass fiber and mounted in the Debye-Scherrer camera for X-ray diffraction analysis. Concentration of the etchant, and also etching time, had to be increased for several of the samples. Fig. 1 shows two extraction replicas taken from different areas of spec. M74-37; X-ray analysis showed a strong diffraction pattern of M23C6 and a medium one of u phase. A

Jan 1, 1962

By John Henry Harden

WITH imperfect instruments it is impossible to make accurate surveys; the results are inaccurate maps, with their attendant consequences. The design of the writer is to describe an improved form of tripod head, and certain defects in an English transit and a miners' dial, with the method taken to remedy the defects of the transit. When the present transit superseded the surveyor's compass, there was one special objection brought against it, and with some show of reason ; namely, that the tripod of the compass with its ball and socket motion, allowed a quicker levelling-up (and, consequently, more work) than was possible with the transit. To this objection it was replied, that the ball and socket would not allow the instrument to be levelled with the same degree of precision that could be attained with the levelling screws, and that if time was sacrificed greater accuracy was attained. Nevertheless, it is a well-known fact that in this country, and especially in England, the compass or miners' dial holds its ground solely from its rapid adjustment. Ever since the introduction of the transit, efforts have been made to give to this instrument the same facility of levelling possessed by the compass or dial, and the same means have been tried, i. e., a . ball and socket motion, since a modification of this in some form was the only method that would answer. The upper part of a transit is, however, much heavier than the corresponding parts of a compass, and, therefore, requires more binding power, which cannot be ob¬tained with an ordinary ball and socket joint. It has been a study with instrument-makers to combine the facility of these two tripods -the quickness of the ball and socket with the steadiness and accuracy of the screws; but in all attempts in this direction the ball and socket of the compass has been literally followed, the entire stability of the instrument depending upon the friction of the ball in its socket. There is great need for a tripod that can be more easily manipulated than the present form, for it rarely happens that an engineer has a level surface on which to set his instrument, and very often

Jan 1, 1879

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts' method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts' method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts' law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts' law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts' law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts' law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By R. W. Cahn, C. D. Graham

Two predictions of the oriented growth theory of recrystallization textures have been tested by measuring the orientation dependence of the rate of growth of a single grain into a strained single crystal of aluminum, and determining the orientations of artificially and spontaneously nucleated grains growing preferentially into strained aluminum single crystals. Growth rates are found to be insensitive to orientation, except that new grains with orientations similar to the matrix or to a twin of the matrix have very low mobilities. Similarly, new grains growing preferentially into a strained crystal have random orientations, except that orientations near that of the matrix or its twins are avoided. The predictions of oriented growth theory are thus not confirmed. BASICALLY, the oriented growth theory of re-crystallization textures1 rests on the assumption that the rate of growth of a recrystallizing grain depends strongly on the orientation of the growing grain relative to the strained matrix into which it grows. In particular, the theory holds that in face-centered-cubic metals the orientation which corresponds to maximum growth rate is one in which the growing grain and the matrix are related by a rotation about a common <111> direction. The amount of rotation, as derived from several kinds of experiments,2-1 has been assigned various values, generally in the range between 20" and 40". (A <111> rotation of 60" is a twin relationship.) The conclusion that boundary migration rates depend strongly on orientation is based almost entirely on indirect evidence; there have been very few direct measurements of boundary migration rates as a function of orientation.* " The present investigation was undertaken to provide such measurements, to help make possible a decision between the oriented growth and oriented nilcleation theories of recrystal-lization textures. The basic experimental program consisted of measuring the rate of growth of a single recrystal-lizing grain consuming a strained single crystal, with the orientations of both grains preselected so that the effect of orientation on growth rate could be determined. A prerequisite for such an experiment is a strained single crystal which will support the growth of a new grain but which will not spontaneously nucleate new grains on heating. That is, the crystal must support the growth of a grain nucleated artificially, but contain no recrystalliza-tion nuclei which will become active at the testing temperature. Beck was apparently the first to note that such a condition could exist," and to make use of the condition for am experiment of the type described here.&apos; The present work was actually suggested, however, by a report of Tiedema". " that an aluminum single crystal strip, oriented with a (111) plane in the plane of the strip and a < 112> direction parallel to the tensile axis, would not recrystallize after 20 pet extension even when heated almost to the melting point, provided that the strip was heavily etched before being heated. This result could not be duplicated in the present work. In fact, it was found that any crystal which deformed in multiple slip (<100>, <112> and <111> orientations) underwent spontaneous nucleation after 15 pet extension, even if etched. However, crystals which deformed in single slip, and which did not develop heavy deformation bands, could be extended 15 pet without showing spontaneous nucleation at temperatures up to 600°C. Crystals oriented within about 10o of <110> which developed heavy deformation bands could be extended 10 pet without showing spontaneous nucleation. In all cases a heavy etch was required to prevent nucleation. Etching was necessary because of the presence of an oxide layer on the crystal surface at the time of straining, which leads to preferential nucleation at the surface.&apos;&apos; Grain Growth Rates Experimental Procedure and Results—Aluminum strips of 99.6 pet purity (principal impurities 0.19 pet Fe and 0.12 pet Si), 1 mm by 1 cm in cross section, were grown into single crystals of controlled orientation by the strain-anneal method of Fuji-wara.&apos;"&apos; " A sharp temperature gradient was maintained in the strips during growth by lowering them into a salt bath controlled at 650°C. Crystal orientations were determined by the etch-pit method of Barrett and Levenson" to an accuracy of ±2O. The crystals were extended by 10 or 15 pet in a simple hand operated tensile machine. Crystal orientations were rechecked after extension, and were found to be in agreement with the orientations predicted by the formula of Schmid and Boas." After extension, the grip ends of the single crystal specimen were cut off with a jeweller&apos;s saw, and the crystal heavily etched (at least 20 pet wt loss) in hot 10 pet Na or KOH solution. A region of severe local deformation was then introduced at one corner of the strip, usually by cutting off the corner with shears. Heating this end of the strip caused a large number of new grains to nucleate at the sheared edge. One of these grains grew to occupy the full width of the strip. The appearance of the strip at

Jan 1, 1957

Allan Gibb, Queensland, Australia (communication to the Secretary*):—It is gratifying that Mr. Edward Keller,&apos; who has clone so much work elucidating the principles of copper-metnllurgy, should have subjected only that portion of our investigation relating to magnetic iron oxide to anything like adverse criticism. Situated as we were on a rnining-camp, it was impossible to undertake work that would cover all the intricate possibilities connected with the materials commonly classed as matte. We therefore began the investigation on matte produced from ores that contained no other components than the sulphides of copper and iron that would be likely to enter into the composition of matte. We were, accordingly, free from ally possibility of magnetic iron oxide entering the matte, unless it were formed in the operation itself. The work done on this subject was incomplete, and the results thereof recorded as giving only negative evidence as to the absence of magnetic iron oxide. It would have been better to have left the matter open, as " not proven." The trend of the investigation was to account for the insufficiency of sulphur in matte to satisfy the requirements of ferrous and cuprous sulphides. So far as our deductions are correct, it was unnecessary to consider the (in our samples) somewhat doubtful constituent, magnetic iron oxide. The mattes that mere investigated were among those mentioned by Mr. Keller, " which scarcely show ally magnetic property." The samples showed no such property. There was no unaccountable variation in the specific gravity, which only varied, as would be expected, with the proportion of ferrous sulphide. I have had experience in smelting ores of which the gangue was a siliceous magnetite, both in blast- and rever-beratory furuace. The mattes so produced contained magnetic

Jan 1, 1908

By C. C. Furnas, S. P. Kinney

The efficient operation of a blast furnace depends primarily upon efficient contact between the descending streail1 of solid materials and the ascending stream of gas. A program of research dealing with the interior of the present-day furnace is being carried by the U. S. Bureau of Mines along two lines: (I) observations on commercial furnaces and (2) experiments in the laboratory. Through the courtesy of the officials of the Illinois Steel Co. it was possible to make a detailed investigation of the interior of the shaft of NO. 4 furnace at the company&apos;s South Works, South Chicago, Ill. The experimental work is reported in a IT. S. Bureau of Mines bulletin&apos; which will include the results of several thousand observations on the interior of the shaft of this furnace. Such of the data as are presented later in this paper constitute only a brief summary. The second part of the work has been conducted in the laboratory. Only one phase of the laboratory investigation has been completed at the present time, namely, the flow of gases through beds of broken solids." The object of this papcr is to correlate the results of the two different lines of research and to present a. more or less complete picture of the condition of the interior of a blast furnace by giving approximate, quantitative data of the actual size-distribution of solid particles in a typical furnncc, and of the efficiency of contact between the gas and solid phases. With such data before him the operator or the experimenter not only has a much better idea of the actunl conditions inside a furnace, hut he also knows in what direction to look for possible improvement. The discussion which follows presents only a few of the items studied and reported; those persons who are particularly interested in all the result&apos;s of this investigation must refer to the aforementioned publication.

Jan 1, 1929

By W. Rostoker

A STUDY of the titanium-oxygen system&apos; involved an associated series of measurements of the lattice parameters of the a and TiO phases. The results permit some interesting deductions which are herein reported. A comprehensive survey of the physical PI-operties of the phases in this alloy system has been made by Ehrlich.2 However, only impure titanium was available at that time, so that some revision of his measurements is to be expected. The lattice parameters were calculated from the high angle lines of Debye-Scherrer patterns taken in a 14 cm camera and using filtered CuKa radiation. The specimens were prepared largely by crushing and screening of lump samples which had been quenched from elevated temperatures. Only in the case of low oxygen contents was it necessary to resort to filing and annealing. The results of the lattice parameter studies are graphically presented in Figs. 1 and 2. It will be seen that oxygen produces a pronounced distortion of the c parameter of the a phase (hexagonal close-packed). The trend is in general agreement with Ehrlich&apos;s work, although the divergence of actual parameter values strongly suggests that his titanium was very impure. It will be noted that the a phase of titanium can tolerate the unusually high saturation solubility of about 34 atomic pct 0. By virtue of this unique effect, it is possible to make a calculation of the effective atomic diameter of oxygen when dissolved in a lattice with metallic bonding. This has not been possible before. Ehrlich&apos;s2 density measurements demonstrated that oxygen occupies interstitial positions in the a lattice and the trend of the lattice parameters would certainly support this. In a hexagonal close-packed unit cell the largest interstitial positions lie at (2/3, 1/3, 1/4) and (2/3, 1/3, 3/4). Accordingly, if both of these positions were occupied, the ratio of titanium to oxygen would be 1:1. The extrapolated c parameter may be taken as between 4.93 and 4.99?. The a parameter appears to reach a constant value of 2.955? at low oxygen contents. The distance of the center of a titanium atom site from the [vc2/16+a2/3-1.448] Then the atomic diameter of the oxygen atom is represented by the function: where the radius of the titanium atom is 1.448A,

Jan 1, 1953

By B. Chalmers, Stefan Wojciechowski

Rotary oscillation of the mold has been used to produce mechanical stirring of the melt during unidirectional solidification. Al-Cu alloys (1 to 4 wt pct Cu) were solidified to study the influence of alloy composition, temperature at which intensive cooling was initiated, and intensity of stirring on the temperature distribution in the sample, the resulting structure, and the copper microsegregation at the columnar to equiaxed transition. The Proposed explanation for the equiaxed solidification in stirred castings consists of the melting off of dendrite fragments, their partial remelting in hotter liquid, and the subsequent growth of the surviving part when the temperature of the melt is lowered. This may result in the formation of a crystal network, which can stop the growth of the columnar crystals and produce the equiaxed zone. It has long been known and many times affirmed that ultrasonic vibrations or relative motion of liquid and solid can significantly reduce the length of the columnar zone and refine the grains in the equiaxed zone in ingots and castings. Because of the technological importance of these phenomena many investigations have been conducted in which ultrasonic energy or mechanical vibration,1-6 electromagnetic stirring,7"10&apos;17 magnetic stirring,"&apos;12 or mechanical stirring13&apos;14 were used to produce the relative liquid-solid motion. More recently, the question of the importance of natural (or thermal) convection has been raised.15-l7 Several possible mechanisms have been suggested.l,8,18-20 They can be divided into two main groups. The first group includes such nucleation hypotheses as nucleation frequency enhancement due to cavitation at the mold wall or other surfaces; cavita-tion in the body of the liquid resulting from the pressure wave, or an agglomeration mechanism, which involves the formation of nuclei by the accretion of subcritical nuclei. The second group considers the grain-refining action to be due to crystal multiplication phenomena such as the removal of the dendrite fragments by viscous forces or by a high-pressure cycle following cavitation or by a melting-off process. Sbme recent investigations give good experimental support to the melting-off proposa1.21-23 The purpose of the present study was to examine the effect of mechanical stirring during the unidirectional solidification on the structure of alloy samples and on the solidification variables. The motion of the liquid was produced by rotary oscillation of the mold around its vertical axis.

Jan 1, 1969

By Edward Keller

In order to conduct intelligently the sampling of copper of various forms and grades, solid or in molten furnace-charges, a knowledge of this subject is essential. Yet figures and tests have been persistently withheld from publication, and the books at our command give us little or no information in this regard. This gap in our copper-literature has led to a series of experiments, the results of which are given below. Nearly all gold- and silver-bearing copper, destined for shipment, is cast into the form of bars or pigs. For the sampler, the question arises, Does copper, so cast, remain homogeneous ? If it does, sampling should present no difficulties; but, from experience, we know that this is not the case, and we are thus led to study the behavior of the precious metals arid impurities in copper when the latter changes from the molten to the solid state. For the purpose of the experiments here described, all available grades of copper were selected, and all of them mere subjected to the same conditions, an important requisite for proper comparison. The molten copper obtained directly from reverberatory- and blast-furnaces was cast in a cast-iron mould, the sides and bottom of which were 1 inch thick, and would, therefore, give the copper a fair length of time to chill. The inside dimensions of the mould, and, consequently, of the block of copper obtained, were: length, 10 inches; width, 9 inches; and depth, 5 inches. Fig. 1 illustrates the method employed to obtain samples from these blocks. A was cut away, and the face so produced BALTIMORE COPPER WORKS,

Jan 1, 1898

By T. E. Scott, D. H. Sherman, C. V. Owen

It has been established&apos; that vanadium exhibits a ductile to brittle transition temperature which increases with increasing hydrogen content. Optical microscopic examination at room temperature revealed no evidence of hydride precipitate in fractured specimens containing 100 ppm H, but hydrides were present in samples with 800 ppm H. More recently2 the strain rate and temperature dependences of the ductility drop in vanadium containing 6 ppm H were reported. It was argued that the ductile-brittle transition, while dependent on the presence of hydrogen, probably could not be explained by the precipitation of hydride. The bases of the argument were that 6 ppm H would not produce sufficient hydride to alter the ductility to the extent observed and no visual evidence of hydride was obtained. However, the data were not sufficient in these investigations 1,2 to define accurately the ductile-brittle transition temperature. Also, no information was available concerning the terminal solubility of hydrogen in vanadium at the low concentrations employed. westlake 3 has studied the electrical resistivity of vanadium at several hydrogen concentrations. He was able to detect the precipitation of hydride and to extend the hydrogen solvus to the composition and temperature range pertinent to the observed ductile-brittle transition behavior, Westlake compared his

Jan 1, 1968

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&apos;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&apos; 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&apos;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-&apos; 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 Robert D. Pehlke, Kazuhisa Okajima

ThE prediction of the activity coefficient for a solute in a multicomponent liquid metallic solution based on measurements in the related binary systems has been the object of study for some time, particularly in iron-base alloys.1,2 Very few measurements, however, have been made on nonferrous systems; furthermore, measurements made for the specific purpose of testing various prediction equations are almost nonexistent. The measurements here described of the activity coefficient of cadmium in liquid lead alloys were directed toward this goal. One of the most direct means by which the activity coefficient can be calculated has been based on the independent influences of each solute. When solute metals i,j, k, and so forth are present, the activity coefficient, y, of one of these (i for example) may be expressed as a product of factors which represent the effects of each of the other components:

Jan 1, 1964

By Robert T. Walker

Robert T. Walker and Woodville J. Walker (Walker Engineering Corp., Salt Lake City)-Mr. Kinkel&apos;s article embodies, in condensed form, the results of the first detailed and complete geological survey that has ever been made of the long neglected but potentially very important West Shasta Copper-Zinc district, in Shasta County, California. In view of the difficulties of the terrain and the complexity of the geological structure, this represents a notable achievement, and it is with regret, therefore, that the writers find it necessary to differ from Mr. Kinkel&apos;s conclusions on two important points. The first has to do with the interpretation of two members of the stratigraphic column of formations in the district; for purposes of comparison, the description of these two members according to Mr. Kinkel is shown parallel to the description of these members according to the writers, see Fig. 14, Mr. Kinkel&apos;s nomenclature being used

Mar 1, 1956

By J. A. Marton, N. Brown, M. Herman

AT high temperatures a deformed polycrystalline metal shows grain-boundary displacement in preference to slip lines.&apos; This has led to the conclusion that overall strain at high temperatures is produced chiefly by grain-boundary displacement. Detailed microscopic examinations of individual grain boundaries have shown many interesting ways by which their displacement occurs; sometimes no grain deformation was observed except possibly in the immediate neighborhood of the boundary. However, X-ray examinations show that at high temperatures subgrain formation occurs;Y he process, generally called polygonization, results from lattice bending and the subsequent climb of dislocations to form low-angle boundaries. Quantitative measures of the grain-boundary displacements show that they make a minor geometrical contribution to the overall strain; the major contribution is made by grain deformation."&apos;" A relationship between grain-boundary displacement and grain deformation was suggested by McLean, who showed how the degree of polygonization would determine the amount of grain boundary displacement: and by Dorn, who showed that for a given creep stress, the amount of grain-boundary shear was related to the overall strain and was independent of temperature.&apos; Although the grain-boundary displacement may make a small geometrical contribution to overall strain, it may still be the rate-controlling factor in high-temperature creep. If in general grain-boundary displacement and grain deformation are dependent quantities, then the designer of a creep-resistant metal would like to know whether it is more desirable to strengthen the matrix of the grain or to increase the strength of its boundary. The widespread interest in the relationship between temperature and grain-boundary displacement makes it desirable to test the generality of Dorn&apos;s result6 that the ratio of grain-boundary displacement to overall strain is independent of the temperature for a given creep stress. In this investigation p-brass was used because it produces sharp grain-boundary displacements above 400°C. Since B-brass undergoes an order-disorder transformation which abruptly strengthens the grain, it is an excellent metal for determining whether grain-boundary displacement or grain deformation is the rate-controlling factor in creep. The problem will be confined to the temperature range where

Jan 1, 1958

J. M. HARTMAN, Philadelphia, Pa.: Mr. Fackenthal can remember some queer things that occurred at Durham, Pa., Aug. 3, 1876, while he was superintendent. The furnace was working stiff, i.e., blast-pressure 10 to 11 pounds, which was high pressure for those days. With this pressure there was some circulation through the stock. At 9 p.m., flushed cinder. After flushing, air was thrown off&apos; for a moment to " bot up "; the keeper turned the lever and threw on air just as the scaffold dropped, which eased up the pressure to 4¼ pounds. The air-receiver is twice as large at Durham as at other places. The air from this receiver, added to the two seven-foot blowers, gave an extra large volume, which, rushing into the furnace, fired the finely-divided carbon, causing an explosion that threw part of the stock in the furnace out into the open air, threw up the bell-and-hopper with the tunnel-head plates, and gave off&apos; a large volume of carbondust. The bell-and-hopper going up first, the stock followed, and, striking the bell-and-hopper, was deflected in a shower over the cast-house roof, breaking the slates. Sitting at the corner of the engine-house at the time, the stock pelted me, when I ran around the corner to get rid of it. Remembering there were two men at the furnace-top, I shut down the engines, and, running to the top, found them sitting in the hoist-house enjoying the fire-works. The explanation of this explosion is simple. There is in the blast-furnace a bed of fuel extending up, say, 16 to 18 feet above the tuyeres; in this bed of fuel some stray pieces of limestone are found, and a few pieces of unreduced ore; but, generally speaking, it is all fuel. On this bed of fuel is the zone of fusion. In this zone the descending stock is liquefied, except the fuel; the iron, melting, drops out of the ore, and the gangue unites with lime, forming cinder. The iron falls in the form of shot, and, with the cinder, trickles

Jan 1, 1899

By C. H. Herty

The elimination of metalloids in the open-hearth process depends on oxidation of the metal by diffusion of FeO from the slag (or absorption of FeO by the metal), with subsequent reaction between dissolved iron oxide and the metalloids carbon, manganese, phosphoms, and silicon. During an investigation on deoxidation with silicon, data on rate of oxidation of the metal were obtained, and these combined with certain other information, are presented here in an attempt to show the fundamental principles governing the diffusion of FeO from slag to metal. Inasmuch as the aim of the investigation was not a study of diffusion, certain data are lacking and it has been necessary to make assumptions on metal viscosity and effect of temperature on diffusion. These factors are known to exert a considerable effect on diffusional processes. Overoxidation, or supersaturation of the metal with iron oxide, is not taken up in this paper. Overoxidation has little effect on diffusion except under a few special conditions, and the discussion has therefore been limited to diffusional processes. Though the results given in this paper should be regarded as preliminary, certain of the conclusions drawn are definitely applicable to any steelmaking process. Previous Study of Absorption An extensive study of absorption has been made by the Department of Chemical Engineering, Massachusetts Institute of Technology. The results are of such direct interest in the problem of slag-metal reactions that it is feIt worth while to summarize them here. The following quotations are from Lewis and hitmman.1 The reader need simply substitute "slag and metal" for "gas and liquid," with proper modifications to take into account the variations in physical properties of

Jan 1, 1929

By P. H. Dudley

When we see the magnificent passenger-trains of from 8 to 12 coaches, drawn by locomotives weighing from 100 to 110 tons, at speeds of from 50 to 60 miles per hour between terminals, to make a schedule of 45 miles per hour, and freighttrains of from 50 to 75 cars of 60,000 pounds capacity, drawn by one locomotive, it is hard to realize that it lacks a few months of fifteen years since my pioneer 5-inch 80-pound rail for the United States was laid by the New York Central aid Hudson River Railroad Co., in July, 1884, on the Harlem line. Shorter passenger-trains, of from 4 to 5 coaches, are run much faster, notably the Empire State Express, the schedule of which for the 440 miles between New York and Buffalo requires 53.3 miles per hour, calling for a running-speed, for much of the time, of from 65 to 75 miles per hour, while higher speeds are very common. On other railroads laid with my 5 1/8-inch 80-pound rail, speeds of from 60 to 75 miles per hour obtain in daily practice. On many of the important railroads east of the Mississippi high speeds of from 60 to 70 miles per hour are part of the daily service. So many instances of speeds of 90, and even 100, miles per hour have been recorded that they must be considered as likely to occur on important lines, and provision must be made for them in the track. Solid mail-trains of from 6 to 8 cars are run from New York to Chicago, 1000 miles, in twenty-four hours; and, commeneing with the present year, shorter trains are running from Chicago to San Francisco, 2000 miles, in three and one-half days. In the freight-service equally important progress has been

Jan 1, 1900

By N. Christensen, B. Augland, T. H. Johansen

Samples of an Fe-Nb alloy were brought to equilibriurtr with hydrogen-methane mixtures in the temperature range from 950° to 1050°C, and subsequently analyzed on their carbon contents. The solubility pvoduct L = [%Nb] [%C] may be represented by the equation Approximate solubilities indirectly assessed through hardness measurements have been included from a previous report. These data are shown to be in a fair agreement with the present solubility measurements. IN an investigation based on hardness measurements by de Kazinczy, Ms, and pachleitnerl the molal heat of solution of NbC was estimated to 11.5 kcal per mole. This value was considered rather small, and an investigation using a similar technique was carried out. The results indicated a heat of solution about 35 kcal per mole.2 At this stage it was decided to determine the solubility under conditions of true equilibrium . During the course of this work a similar investigation was published by Smith. 3 His heat of solution, 41.6 kcal per mole, is not very different from the value resulting from the present work (42.5 kcal per mole). Our solubility product, on the other hand, is at considerable variance with that reported by Smith. Possible reasons for these differences are discussed below. Mori, Tokizane, and saheki 7 have studied the behavior of niobium in commercial steels, with special attention to the formation of niobium carbide, nitride, and sulfide. Assuming a carbide composition Nbco.87 based on X-ray diffraction and chemical analysis of residues extracted from Fe-Nb-C-S alloys, the molal heat of solution of niobium carbide was estimated to 35.2 kcal per mole. MATERIALS AND EQUIPMENT The chemical analysis of the materials is given in Table I. Electrolytic iron* was used in the preparation of

Jan 1, 1968

By C. E. Birchenall, R. H. Condit

THREE surface activity procedures are in com--L mon use for the determination of diffusion coefficients in solids. In the oldest of these&apos; the activity observed at the original surface is compared before and after diffusion, where all the activity is in a thin, plated layer on the surface before diffusion. Partial absorption of the radiations from active atoms which have diffused below the surface reduces the effective activity after diffusion. The formula employed to calculate the diffusion coefficient is where F, is the ratio of final to initial activity at the surface, measured with identical counting geometry; Z=u3Dt, where D is the diffusion coefficient; t is the diffusion time; and u is the absorption coefficient for the radiation in the solid as defined by Lambert&apos;s law. This absorption law implies that all the rays are parallel to each other and normal to the specimen surface. This assumption of a collimated beam used by Steigman, Shockley, and Nix has been adopted by all other investigators and, although it gives results which are approximately correct under restricted physical conditions, it does not represent many actual circumstances. It is the purpose of this paper to show the importance of the divergent rays and to indicate a procedure for taking them into account. In the residual activity method the activity is determined on a series of surfaces ground on the specimen at progressively greater depths in the diffusion layer parallel to the initial surface. Gruzin2 has de- rived a formula for this procedure, which may be put in the form where I is the ratio of the activity measured at a newly ground surface at distance k below the initial surface to the activity at the initial surface measured after diffusion, and K= k/2p Dt. A third procedure involves the autoradio-graphic determination of activity on a plane ground at a small angle to the initial interface through the penetration zone. Aut oradiography can be particularly sensitive to the oblique rays. Unlike most counters which detect essentially all ß particles or X-rays which enter the active volume as a single event, the photographic emulsion may be thin enough so that oblique rays with longer path length in the emulsion produce more darkening than rays which move normal to the film plane. Consider a plane containing a source of radiation uniformly spread over a circle and a point counter located on the perpendicular through the center of the circle. As the counter moves along this line, the total angle 6, at the counter subtended by the specimen will vary. For a fixed counter distance, let 6 be angle between the counter axis and the line connecting the counter to a point P on the active plane. If an absorber of thickness X is interposed parallel to the source between counter and source, the ray from point P to the counter will pass through an absorber thickness X secant 6. Exponential absorption is assumed to hold for all rays. If r, is the ratio of intensity at the counter with absorber to the intensity without absorber and a = pX, 1 00 The behavior of this integral, evaluated numerically,

Jan 1, 1957