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By Marie L. V. Gayler

WITHOUT diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange-e.g., of diffusion-is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult-if possible to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, ßFeSi is formed in the solid as the result of the reaction aFeSi + Al?ß FeSi. The particles of aFeSi become sur¬rounded with a reaction ring of ßßFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of ßFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

For the year ending February, 1936 PRESIDENT AND DIRECTOR HENRY A. BUEHLER ROLLA, Mo. PAST PRESIDENTS AND DIRECTORS FREDERICK M. BECKET NEW YORK, N.Y. HOWARD N. EAVENSON PITTSBURGH, PA. VICE-PRESIDENT, TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y.

Jan 1, 1934

S. Tandanand, Twin Cities Mining Research Center, U. S. Bureau of Mines As an addition to the fine reviews on drilling presented in the foregoing papers, we feel it would be appropriate to mention briefly some work in this area by the U. S. Bureau of Mines. The Bureau has had under way for several years at its Twin Cities Mining Research Center studies directed toward a better understanding of basic drilling mechanisms. The work includes drillability investigations with diamond rotary, and with percussive drilling systems, as well as fundamental studies of rock behavior under drill bit types of loading. Results of our work to date have contributed the following to the state of the art. MECHANISM OF ROCK FAILURE-Rock fragmentation through use of mechanical energy systems, including drilling systems, consists of two major components-machine and rock. The two components are related to each other by their functional behavior and their resultant motion which the components mutually influence. Forces in the systems are transmitted directly to the bit which in turn induces stresses in the rock. When the induced stresses exceed the strength of the rock, the rock fails resulting in penetration. Rock strength is a function of the forces applied to the rock. Stresses under a drill bit, regardless of bit configurations, are essentially compressive, resulting in a condition where the rock has the highest resistance to failure. The ratio of principal stresses induced under drill bits is an indication of the mode of failure in the rocks. Initially, compressive stresses under the drill bit cause rock to undergo inelastic deformation. The impression observed at the first stage of crater formation under the drill bit shows that rock is no longer elastic. Associated subsurface failure at this stage precedes total rupture which subsequently appears at the rock surface. Thus, explanation of crater formation, by applying theory of elasticity alone, is likely to be over-simplified. ENERGY VERSUS VOLUME OF ROCK REMOVED-Experimental results show that energy per unit volume of rock removed is constant for a particular rock and bit type. Rock offers a definite resistance to penetration, depending on the method of the energy application; this may be defined as the drilling strength of a rock. Energy consumption in a drilling system may be divided into two components: 1) Energy required to move the machine parts; and 2) energy consumption in breaking rock. Component 1 is dependent on the type of the machine. Component 2 is dependent on the strength properties of rock and the efficiency of the bit in rock cutting. The sum of the energy required in both components determines the total energy required in breaking rock. Our work in this area has included consideration of both diamond and percussive drilling systems. PENETRATION RATE-For a drilling rate expression to be useful in predicting field performance, it should include the operating characteristics of the drilling machine. Eq. 37, for example, is simply a statement of the fact that the drilling rate is determined by the power output of the machine (2pNT) and the power requirements to break the rock in the hole (AER). In order to predict the performance of a particular drill and the effect, for example, of the rotary speed, on the drilling rate, R, Eq. 37 must be modified to include the

Jan 1, 1967

By G. Rinelli, A. M. Marabini

Flotation of rutile with N-benzoyl-N-phenyl-hydroxyhmine (N-BPHA) has been investkated. Initially, floatability tests were performed in a Hallimond tube. The results indicated that rutile was floatable at pH 2-4 with N-BPHA concentration between 2 x 10-3 mol/L and 2 x 10-2 mol/L. Selectivity against hematite was recognized when operating at pH values below 2. Following the hypothesis of the formation of a surface chelate between N-BPHA and titanium ion, this compound was precipitated from a solution of Ti (SO4)2 to which N-BPHA was added. I. R. spectrometry of the rutile before and after treatment with N-BPHA solution confirmed the presence of this compound on the rutile surface. Adsorption isotherm and kinetics were determined by analyzing N-BPHA in solution with an U. V. technique. A hypothesis on the way N-BPHA is adsorbed on rutile is presented.

Jan 1, 1984

By O. F. Walker, W. C. Hahn, V. A. Johnson, J. D. Wood

The diffusion coefficients of zinc in single-crystal zinc and carbon in single-crystal and poly crystalline nickel were measured by means of radioactive tracer techniques both with and without the application of ultrasonic vibrations under conditions such that the temperature of the sample was closely controlled. The results of this investigation indicate no enhancement of diffusion in any of the samples. It is suggested that previously reported enhancement may have been due either solely to temperature increases caused by ultrasonic vibrations or in combination with changes in the boundary conditions. A number of observations have been reported in the literature in which it has been implied or inferred that the application of ultrasonics enhances diffusion (see, for example, Refs. 1-5). The present study was undertaken in an attempt to observe this effect under carefully controlled conditions, particularly with regard to measurement and control of the temperature of the sample. Two different types of systems were studied; these were the self-diffusion of zinc and the diffusion of carbon in nickel. EXPERIMENTAL For diffusion with ultrasonic energy applied, the samples were included as part of a resonant ultrasonic system operating at 58.5 kcps. The ultrasonic generators used were rated at 100 and 250 w and could be tuned over a frequency from 10 to 100 kc. A PZT (lead titanate/lead zirconate) ceramic transducer provided the driving vibration. This system requires no metallurgical joining of the specimen to the acoustical transmission line since the ultrasonic driver and the follow-up section clamp the specimen in position by means of a constant pressure of 50 lb developed by an air cylinder. The ultrasonic driver and follow-up section, both made of titanium, were 4 in. in length from clamping point to the end in contact with the specimen. Using the relationship given by Mason,6 A = V/f, the resonant wavelength, A, in titanium is calculated to be 3.3 in. at a frequency, f, of 58.5 kc, taking the velocity of sound in titanium, V, as 1.95 X 105 in. per sec. The 4-in. driver and follow-up section, therefore, are each 4.0/3.3 =1.21 times the resonant wavelength. Clamping pressure must be applied at stress nodes of the transmission line in order to preserve resonance. Therefore, a specimen length of 0.58 times the wavelength in the specimen was required to place the clamping pressure application points at stress nodes exactly three wavelengths apart. A stress antinode was contained in the center 3 in. of the specimen. A small PZT ceramic disc attached to the follow-up section provided an output voltage proportional to the intensity of the standing wave. This output voltage was monitored on an oscilloscope and the ultrasonic system was tuned to resonance by varying the frequency until the output signal was a maximum amplitude. The amplitude of the output signal was maintained constant throughout the diffusion anneal. A split cylindrical stainless-steel chamber, which was purged with argon prior to and during the runs, was placed around the specimen. The chamber in turn was surrounded by a movable furnace whose temperature could be controlled to 7C. Heat exchangers were used to cool the driver, follow-up section, and ultrasonic transducer. Great care was taken to obtain the true specimen temperature in all cases. Several different methods were tried; the most successful was that in which the thermocouple was held in contact with the midlength of the specimen by means of an asbestos insulating pad and wire straps. In the case of zinc, single-crystal specimens of 99.999 pct purity were used. The samples were 0.25 by 0.25 in. square and of the proper length for resonance, that is 1.1 in. long with the c axis parallel to the long dimension of the specimen for the case of diffusion perpendicular to the c axis and ultrasonic motion parallel to the c axis, and 1.9 in. long with the c axis perpendicular to the long dimension of the specimen for the case of diffusion parallel to the c axis and ultrasonic motion perpendicular to the c axis. In each case, one of the rectangular faces was electroplated with a thin film of zinc containing Zn The constant pressure used to clamp the specimen in place in the ultrasonic system caused some deformation in some of the samples. For these samples the deformation was concentrated in either end of the specimen; thus, for all samples (both zinc and nickel) the center in. was cut from the specimen after the diffusion anneal to be used for sectioning and counting. The nickel single-crystal samples, of 99.999 pct purity, were used in the form of rods 0.25 by 0.187 by 2.07 in. long with the (100) direction parallel to the rod axis. The polycrystalline nickel samples of 99.97 pct purity had an average grain diameter of 0.007 in. and were used in the form of rods 0.25 by 0.125 by 1.87 in. long. The direction of ultrasonic motion was parallel to (100) direction (bar axis) for the single-cqstal samples and parallel to the bar axis for the polycrystalline specimens. A thin film of c14 suspended in methanol was applied to the diffusing face of the specimen. Two specimens were butted together lengthwise for each diffusion anneal to minimize oxidation. After diffusion, a precision lapping device similar to the one described by Goldstein7 and a radiation detector were used to obtain a plot of specific activity vs penetration distance for each specimen. (A scintil-

Jan 1, 1969

The State School of Mines, University of Utah, is this year giving-a four weeks' course for prospectors-Jan. 8 to Feb. 3, 1917-covering the fundamentals of geology, mineralogy, mining and the metallurgical treatment of ores. There will be 36 lectures of 1 hr. each and about 20 laboratory periods, each 3 hr. in length. It is the purpose of the School of Mines to make the course entirely a practical one, and purely theoretical considerations will be omitted. The laboratory work is designed to supplement the lectures and-to give those taking the course a working knowledge of the principles involved. In order to bring the course within the reach of all, no laboratory fees will be charged, and the only fee will be a nominal one for registration in the University, of $1.00, but it is expected that those who attend will be genuinely interested in the work.

Jan 2, 1917

By G. Aertsen

THE CHAIRMAN (HENRY D. HIBBARD, Plainfield, N. J).-This excellent paper fills a gap in our Transactions and is most acceptable. In the early days another way of casting tire ingots, sometimes called cheeses, because of their shape, was to use a 22-gage sheet-iron cylindrical can for each ingot of the proper size to give the weight desired. These cans were bottom cast in groups, usually of four, each can being surrounded by a heavy iron ring somewhat taller than itself the top of the can being covered by a circular cast-iron plate having a small conical riser in the center, about 2 ½ in. in diameter at the bottom and 10 in. high. The top plate was clamped down to resist the upward pressure of the fluid metal and the space between the can and the outer ring, usually about 2 in. wide, was filled with dry sand. The riser permitted the escape of some of the air displaced by the steel and also increased the pressure in the steel when the mold was filled, and so diminished somewhat the tendency for gas holes to form. But little was known of segregation and pipe in those days, though the center of an ingot was understood to be the worst part, and it was separated in part in the disk which was punched out in perforating the ingot. This disk was about 8 in. in diameter and from ¾ to 2 in. thick, the variation in thickness being to rectify the weight. When an ingot was too -heavy, a thicker disk-was made by not driving the punch in quite as far as when the ingot-weight was right. Then the bloom was turned over and the punch driven in on the other side, which finished the punching and detached the disk. The tire bloom was then" becked" and later reheated and rolled as described in the paper. The forging was done with a 10-ton double-acting steam hammer. The steel generally speaking had lower carbon, from 0.45 to 0.55 per cent., than tires today have, and the tires were smaller, the most common size of ingot weighing 1,060 lb. each. BRADLEY STOUGHTON, New York, N. Y.-This paper was specially requested by the Iron and Steel Committee, because that Committee thought so important an industry should have its history written by one who was familiar with it, and before he had forgotten, or all the rest of the world had forgotten, its early stages. Mr. Aertsen has said that it is not an exhaustive research. I think it would not be any different if it were an exhaustive research, because our library made a careful attempt to find some written light on the history of these tires, but very little was found.

Jan 4, 1917

By AIME

HAPPILY, a large group of the non-ferrous fraternity have long valued a personal association with the new Chairman of the Institute of Metals Division. Many others who will meet him, either officially or unofficially this year, will find themselves sharing the enthusiasm with which he has been welcomed to his new office. Albert A. Smith, Jr., was born at Butler, N. J., on Dec. 28, 1904, and moved to New Haven in time to initiate his preparation for Yale University on the home grounds. After receiving a B.S. degree cum laude in 1926, he stayed on for graduate work at the Hammond Laboratory under C. H. Mathewson, and was awarded an M.S. degree in 1928.

Jan 1, 1948

[Cyanidation: Fresnillo, Mexico. 112. 734, 739. Abs.. YB84. 34 gold ore: before or after amalgamation. respective merita. 118, 538 high residue avoided by milling in water, 118, 542 Homestake mill, 112,607. 614 impoverishing gold ore before cyanidation justified. 118, 539 Kirkland Lake district, 112, 648, 649. Abs., YB84.32 literature prior to 1932. See Source Book. McIntyre Porcupine mines, 118, 638 mercury as an aid to extraction of gold, 118, 53 8]

Jan 1, 1936

(Members are urged to send in for this. column any notes of interest concerning themselves or their fellow-members.) Members and guests who called at the Institute headquarters during the period Sept. 10, 1916 to Oct. 10, 1916. Arthur K. Adams, Chanaral, Chile. C. F. Moore, Salt Lake City, Utah. Hiram W. Belnap, Washington, D. C. L. D. Moore, Providence, R. I. E. A. Bridgman, Seattle, Wash. George A. Morrison, Chicago, Ill. D. W. Buckly, Wallace, Idaho. Pablo Ortega, Havana, Cuba. G. L. Carlisle, Jr., New York, N. Y. L. W. Paige, New York, N. Y. Ernest H. A. Cohen, Johannesburg, So. Africa. Charles Petzel, New York N. Y. A. Faison Dixon, Camp Rio de Oro, Venezuela. C. A. Pierce, Patagonia, Arizona. Charles E. Dutton, Goldfield, Nev. W. E. Pomeroy, El Paso, Texas. D.-F. Hewitt, Washington, D. C. George S. Rice, Washington, D. C. . James E. Howard, Washington, D. C. G. J. Schofield, Seattle, Wash. A. 0. Ihlseng, Joplin, Mo. Warren D. Thompson, New York, N. Y. I. Ishikawa, Niagara Falls, N. Y. M. M. Valerius, Tulsa; Okla. Montrose L. Lee, New York, N. Y. G. B. Waterhouse, Buffalo, N. Y. V. H. McNutt, Billings, Mont. Joel H. Watkins Washington, D. C. Benjamin L. Miller, So. Bethlehem, Pa. H. P. Wherry, Chicago, Ill. Arthur K. Adams has left for Chile, where he will act as geologist for the Andes Copper Co., a subsidiary of the Anaconda copper company.

Jan 10, 1916

By James Norman

SPODUMENE is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content it might be a desirable constituent of glass batches. The use of spodu-mene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components.1 The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manga-nese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li20 on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston, ? the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3 The methods described in the second publication' did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted.

Jan 1, 1940

By D. H. Newland

During the year 1907 an investigation of the Clinton formation in New York has been carried out under the direction of the State Geologist, and a full account of the results has been prepared for publication.' The more important economic features of the report are summarized in the present paper. Previous knowledge of this, the type, section of the Clinton has been contributed mostly by Hall and Vanuxem in their reports for the Natural History Survey of New York, which were issued in their final form in 1842-43. Brief accounts of the ore-occurrences have been given by 13. T. Putnam? J. C. Smock: A. H. Chester: and E. C. Eckel.5 Prof. C. H. Smyth, Jr.,6 has discussed the origin of the Clinton ores in two papers, which, so far as the local occurrences are concerned, have removed all doubt that may have existed on that subject. Distribution of the Clinton Formation. The Clinton strata in New York State are restricted to a single belt, which extends from the eastern central part to the Niagara river, which it crosses, and thence continues for some distance into the province of Ontario. The New York

Jan 1, 1910

Not many accounts of mining methods or labor conditions in the mines in early days can be found; all that have seemed to be authentic have been included in the preceding chapters. In practically every field opened before 18.10 the first coal was recovered by quarrying, or strip mining, the operations, of course, being by hand and on a very small scale; new places were opened as soon as mining became difficult or expensive. Where it became necessary to drift into the hillsides, the first coal was taken out by sleds, and later by small wagons, the power being supplied by the miner, often assisted by dogs. Wooden rails then came into use with small cars running on them. These cars were very small, usually holding only a few bushels; in the Belleville, Illinois field as late as 1863 cars having capacities of 10, 12, 14 and some as large as 30 bushels were in use. It was not until late in the 1830's that horses or mules came into use for haulage purposes in the Pittsburgh region, although some had been used in the Richmond, Virginia field at an earlier date. Coal was usually undercut by hand and wedged down, until explosives came into general use, and in nearly every field the coal was forked into the cars, the fine coal, or slack, being left in the mine. Hours worked were very long, but few records remain to show what they were at different places and times; there was undoubtedly a great variation between districts and mines. Roy stated a miner could often produce 5 or 6 tons in a day of 8 or 9 hours in a 5 or 6 foot seam, but in another seam possibly could mine only 3 1/2 to 4 tons. He estimated an average day's work in a four foot seam at about 3 1/2 tons.1 In a strike in the Belleville field in 1863 it was found that an average skilled miner in the field could probably produce 4 to 5 tons a day.2 This was only the coarse coal loaded and did not include slack. In 1873, a coal undercutting machine was tried at a mine about two miles from Brazil, Indiana, said to be the first coal machine ever invented in the United States. It was run by a 5 H.P. steam engine (later to be changed to compressed air), and consisted of an iron rim, four feet in diameter with movable steel teeth placed about one foot apart. The rim

Jan 1, 1942

By Charles M. Rolker

It is not my purpose to present a complete description, still less a thorough discussion from a theoretical stand-point, of the Leadville ore-deposits. Hence I have given to this paper the more modest name of " Notes;" since it is little more than a record of observations made three or four years ago, and now published from my original memoranda, with the view of preserving the facts rather than of

Jan 1, 1886

The Petroleum Division met at Fort Worth, Texas, Oct 8-9 $ The headquarters were at the Blackstone Hotel, the attendance was 175 Sixteen papers were presented, 12 of them by the authors The technical program was built up around four major topics. Drilling, Production, Engineering Education and Metallurgy There were four sessions, two each day More than 100 were present at the luncheon on Friday noon, which was addressed in turn by President Lovejoy, George Otis Smith

Jan 1, 1937

Discussion of the paper of E. S. Moore, presented at the Colorado meeting, Sep-tember, 1918, and printed in Bulletin No. 135, March, 1918, p. 687. W. F. SMEETH, * Bangalore, Mysore, India (written discussion ? )-Before dealing with the air blasts, I would like to clear up a geological point. The author states that the matrix of the conglomerate resembles a hornblende schist. This is a, misapprehension. The conglomerate

Jan 10, 1918

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

By J. S. Kirkaldy, G. R. Purdy

THE formation of ferrite in supersaturated aus-tenite has been the subject of considerable speculation and investigation. Aaronson has recently reviewed the data pertinent to this reaction.' Since these data in all cases refer to ternary or high-order alloys it is not possible to put them to the test of simple binary diffusion formalism. It has not, therefore, been possible to make a certain statement as to the controlling mechanisms in the process. An assessment of the difficulties inherent in the conventional statistical metallographic approach suggested that a study of the problem by means of a macroscopic two-phase diffusion couple might contribute useful information. Accordingly, such a couple was synthesized, and the rate of motion of a ferrite-austenite phase boundary (the growth of an austenite layer at the expense of a ferrite layer) was determined. Wagner originally produced a diffusion solution applicable to the motion of a planar phase interface in a binary diffusion couple, assuming local equilibrium throughout the diffusion zone. This solution, which is stated free of typographical error* in Ref. where a is the position of the interface in A space (A = x/fi), C; and CL1 are the equilibrium inter-facial concentrations in phases I and 11, C: and C*1 are the initial bulk concentrations in phases I and 11, and & and are diffusion coefficients (assumed constant). If a diffusion couple consisting of homogeneous layers of ferrite and austenite in equilibrium is raised to a higher temperature, the austenite layer will grow at the expense of the ferrite. Provided that the thickness of the ferrite layer is much less than the diffusion length of carbon in ferrite, we can set , so that Wagner's solution reduces to

Jan 1, 1963

By James C. M. Li

The Petch relation between the flow stress and the gain size is derived from a consideration of gain boundary sources of dislocations without the need of dislocation Pile-ups. Three mechanisms for inierpreting the yield stress: the gain boundary strength, the unpinning of Frank-Read source near a grain boundary, and the generation of dislocations from the grain boundary are compared and the condition of their equivalence is shown. The effect of the average angle of misfit of pain boundaries is found to be sma11 and so is that of the average angle of misfit of subboundaries having impurities. The effect of impurities on the ledge density in the grain boundary is treated thermodynamically and a relatwn is proposed for the variation of Petch slope with impurity activity. The effect of temperature on the Petch slope is interpreted as due to the change of ledge structure in the grain boundary. It is indicated that the effect of annealing temperature may be more important than that of the test temperature and therefore should be studied. The effect of plastic strain on the Petch analysis is deduced from a work-hardening equation in which the generation of dislocations has first-order kinetics and the annihilation of dislocations has second-order kinetics. It is concluded that the Petch slope will decrease with plustic strain if the rate of annihilation of dislocations is sufficiently large. Critical experiments which may shed light on the mechanism for the Petch relation are suggested. THE relation between the yield or flow stress, 0, and the grain size, l, was first proposed by all' and later studied more extensively by Petch and co-workers, who also proposed a similar relation for the fracture stress and deduced from these a grain-size effect of the ductile-brittle transition temperature. The microscopic mechanism used by all' and petch2 involves a pile-up of dislocations of like sign generated from a Frank-Read source. The yielding or flow takes place when the pile-up exerts sufficient stress at the grain boundary so that the plastic deformation can propagate from one grain to another. If the average strength of the grain boundary is ai and the average length of the pileup is lp, the Petch slope, k, is given by" where p is the shear modulus, b the Burgers vector, and v the Poisson ratio. This slope will be independent of the grain size if l/lp is a constant. This is possible, since, if the Frank-Reed source is situated near the grain boundary, lp = 1, and if it is situated in the middle of the grain, Ip = 1/2. cottrell,12 also using the pile-up mechanism, proposed that the stress concentration at the grain boundary will initiate Frank-Read sources near the grain boundary and in this manner a Lüders band can propagate from one grain to another. Assuming that the average distance between the Frank-Read sources and the grain boundary is 1, and the unpinning stress of the Frank-Read sources is op, Cottrell obtained the following Petch slope: This slope will be independent of the grain size if ls is independent of the same, which is not as obvious as the condition, Ip = I for Eq. [2]. In addition to this assumption, the direct relation between the Petch slope k and the unpinning stress, up, was recently questioned by Johnsonon grounds that it is inconsistent with the following observations: the independence of k with temperature and strain rate, and the small k in columbium, which, like iron, has a sharp yield point. As pointed out by ohnson," the most important objection both to the Hall-Petch mechanism, in which the strength of the grain boundary plays the role in yielding, and to the Cottrell mechanism, in which the unpinning of Frank-Read sources plays the role in yielding, is the lack of direct observation of the pile-ups. The dislocation structure in deformed iron has been examined recently in the electron microsope.'-' Dislocations appear to be generated from grain boundaries or other interfaces; they form clusters and tangles within the grain at very early stages of deformation, even in the Lüders band, if the deformation is slow or at normal and elevated temperatures. Although it is still too early to interpret bulk properties from thin-film observations, it does seem worthwhile to look for a mechanism for the Petch relation which does not require dislocation pileup. SUBBOUNDARY SOURCES In order to show that a consideration of grain boundary sources can lead to the same Petch relation as does the consideration of the strength of the grain boundary, we shall first discuss the case of a simple tilt boundary whose elastic properties have been studied in detail.17 The strength of a partially

Jan 1, 1963

By R. A. Corley, W. R. Wilcox, J. R. Teviotdale

Chemical vapor deposition of hafnium carbide yielded whiskers, needles, dendrites, faceted crystals, and adherent coatings. The gas stream compositiom and the mass transfer conditions determined the habit of the deposit. The deposits were obtained at temperatures ranging from 1100" to 1800°C. HAFNIUM carbide has the highest melting point of any binary compound; therefore, its various potential applications are a subject of vital interest to the aerospace industry. The experiments described herein were performed to investigate the chemical vapor deposition of hafnium carbide with particular interest being placed upon the possible production of high-strength single-crystal whiskers for composite materials. In 1931 Moers 1 used a gaseous mixture of HfC14, Hz, and toluene to vapor deposit crystalline hafnium carbide on a tungsten filament heated to 2400°to 2800°C. More recently Lepie 2 deposited hafnium carbide on graphite using HfC14 and methane in a helium gas carrier. The pyrolytic depositions described here were accomplished in graphite tubes by using various gas mixtures and dopants. The resulting crystal habits included whiskers, needles, needle dendrites, bulbous dendrites, faceted crystals, and smooth, adherent poly-crystalline layers. EXPERIMENTAL The depositions were carried out in an induction-heated graphite tube, 1.2 cm ID, which was contained in a vertical 9-cm-ID quartz tube. (A more detailed account of the experimental procedures and results is given in Ref. 3.) Refractory oxide fiber and tubes and graphite felt were utilized jointly and singly for therma1 insulation. A typical temperature distribution is shown in Fig. 1. The reactant gases were introduced at the top and removed at the bottom of the tube. Table I summarizes the experimental conditions and results. Many deposition habits were obtained. X-ray analyses showed that they possessed the hafnium carbide structure. Almost invariably these formed well above the point of maximum temperature in the graphite tube. The habit depended strongly on the gas composition. In a series of runs (e.g., run A) using HfC14 and toluene in H 2, hafnium carbide coatings, Fig. 2, were reproducibly obtained at the position where the tube wall was 1400°C, and bulbous dendrites, Fig. 3, were

Jan 1, 1969