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By B. C. Allen, W. D. Kingery

Surface tension and its temperature dependence have been determined for pure liquid Fe, Cu, Co, Ni, and Sn and for Fe-C, Co-C, and Ni-C alloys. The temperature coefficient of surface tension is negative for all these liquids. The surface tension and wetting behavior of tin and tin-titanium alloys on A120,, Si,N,, MoSi,, and Sic, as well as the behavior of titanium-containing nickel alloys on A1 20, have been determined over a wide temperature range. For all the solids investigated titanium additims markedly lower the contact angle. Some limits for the solid-surface energies have been calculated from liquid surface tension and wetting behavior. SURFACE tension and interface energy are important variables in a number of metallurgical and ceramic phenomena, and have been discussed at some length in connection with determining micro-structure of polyphase systems,' solid-state sintering,' thermal etching of grain boundaries, heats of solution and fine powders,'1 grain-growth phenomena,' the mechanical behavior of fine foils and fibers, nucleation, soldering and brazing,' and other phenomenz of academic or practical interest However, until recently few quantitative data have been available for high-temperature systems. Among available data are some indicating positive temperature coefficients for the surface tension of liquid copper,*,11,'2 cast iron,l3 and iron-carbon14 alloys. Although carbon was found to be not surface active in iron at 1570" some preliminary studies had indicated the possibility of a positive temperature coefficient for the eutectic composition at lower temperatures.16 One part of the present study has been largely concerned with determining the temperature coefficient of surface tension for several metals at elevated temperatures, In addition to surface-tension studies, the wetting behavior of alloys containing titanium has been investigated over a wide temperature range. Previous measurements indicated that titanium was selectively adsorbed from nickel at a liquid nickel-solid alumina interface,17 and the use of titanium hydride or titanium-alloy techniques for metal-ceramic soldering is well known. In the present study, previous data have been extended to new alloy systems, and measurements have been carried out with other oxidation-resistant ceramics. EXPERIMENTAL The sessile-drop method was employed to measure liquid surface tension and contact angle between liquid and solid, utilizing apparatus and techniques which have been described previously.'g The shape of a sessile drop depends on equilibrium between forces of surface tension tending to form a spherical surface of minimum area and forces of gravity tending to flatten the drop. Typical sessile drops are shown in Fig. 1. From precise measurements of maximum drop diameter and drop height the surface tension and drop volume were calculated. Four solid materials were employed as supporting plaques for the liquid-metal drops. Aluminum oxide (99.9 pct, J, T. Baker, reagent grade) was pressed and sintered at 1800°C. Molybdenum-disilicide powder (99.0 pct, Electro Metallurgical Co.) was pressed and sintered at 1650°C. Plaques were cut from silicon carbide (99.4 pct, hot-pressed at Alfred University) and silicon nitride (95.1 pct, with Al, Fe, 0 as major impurities, Norton Co.) rods. All plaques were polished, cleaned, and dried prior to use. A number of metals and alloys were employed. Chemical analyses of vacuum-melted ingots of iron, nickel, cobalt (National Research Corp.), commercial nickel-base alloys, electrolytic copper (International Smelting and Refining Co.), and tin (Mal-linckrodt Chemical Works) are given in Table I. Alloys were prepared in the laboratory by vacuum melting the base metal with either titanium hydride (Metal Hydrides, Xnc.) or spectroscopic-grade carbon (National Carbon Corp.). Nickel-titanium alloys contained between 0.001 and 0.005 pct oxygen and the ferromagnetic metal-carbon alloys contained 0.001 pct. Cylindrical metal specimens (1 to 2.5 g) were machined and bevelled at the bottom to insure a uniform advancing contact angle on melting. Before use the samples were acid-etched, cleaned with acetone, and rinsed in petrol ether.

Jan 1, 1960

By F. C. Langenberg

IT is the purpose of this paper to present a limited amount of experimental data obtained on the Charpy impact machine. Several concrete examples will be given showing the relation existing between the results obtained upon the Charpy impact machine and the behavior of the parts tested when in service. Although it is pointed out by G. Charpy and A. Cornu-Thenard1 that it is first necessary to determine a satisfactory working process before studying the correlation between the results of these tests and the behavior of the parts tested in service, this ideal course cannot be strictly adhered to. If a certain part repeatedly fails in service and the available tests give no indication of its cause, advantage must be taken of any possible means that will solve the problem; therefore, even though the reliability of the results obtained by the Charpy impact machine have been questioned by many, it was necessary to use this instrument without giving careful consideration to its possible sources of error. It would seem that the conclusions arrived at by Charpy and Cornu-Thénard justify the assumption that the precision obtained by this machine is comparable to that obtained by, the other more common forms of testing. The second general conclusion arrived at by them, namely, that the impact test upon notching does not offer any direct correlation to the ordinary tests, is also borne out by many hundred determinations made in the laboratories at Watertown Arsenal. This statement, however, should be qualified as follows: Other ordinary tests include the static tensile test from bars taken in a longitudinal .direction and the Brinell hardness. The author agrees that no law is yet known for the computation of the energy absorbed in the rupture of bars of the same material but of different dimensions. Although Charpy and Cornu-Thénard do not refer in their valuable article to the use of the Charpy machine in industrial practice, it should be stated that this instrument has been in constant use in the laboratory at Watertown Arsenal for several

Jan 8, 1919

By N. Brown

IT has been observed that a hexagonal-close-packed crystal will undergo the same macroscopic displacements as an isotropic material if the basal plane is perpendicular to the axis of twist.&apos; Other orientations may produce both bending and twisting, but this analysis will be confined to pure torsion of a right circular cylinder. The z axis, the axis of twist, and the specimen axis are coincident. The displacements are given by Uq = rz, Ur = Uz = 0 [1] where 4 is the angle of twist per unit length. This requires rotational slip, as discussed by Frank&apos; and Wilman, which may be observed readily. The relative rotation of adjoining slip planes is simply produced by a movement of a planar grid of screw dislocations."." The screw dislocations are of the same sign and they move radially inward. For hexagonal-close-packed metals, the grid is hexagonal and the screw dislocations lie in the < 2110 > directions. The displacement of a point is the resultant of two displacements produced by intersecting screws sweeping over the point. The dislocations must pass over the point (r, o) in such a manner that its resultant displacement corresponds to the observed macroscopic displacement. If 6&apos; is measured from the [1010] direction, then for 0 < ? < ~/3, only the [1210] and 121101 type screw dislocations are needed to produce the required displacement. If n1 screws of type [1210] and n2 of type [2110] pass over a point, then, in order that Ur = 0 n, sin ? - n2 sin (/3 — 6&apos;) = 0. [2] If the tangential displacement is to be independent of 0, then n1 cos ? + n2cos (/3 —?) = N [3] where N is independent of ? and thus depends only on r. Nb is the tangential displacement where b is the Burgers vector. Since U? is a linear function of r, then N must be a linear function of r. If a2 is the outer radius and a, is the inner radius to which the plastic deformation has extended, then N = Nm2 r-a1 [4] This function meets the conditions that at

Jan 1, 1956

Albin, B. R Billings, Mont. &apos;28 Amster, Nathan L 25 Broad St., New York, N. Y. &apos;28 Bache, Jules S 42 Broadway, New York, N. Y. &apos;28 Barrett, C. P 5338 Harper Ave., Chicago, 111. &apos;28 Bayless, William S Russ Bldg., San Francisco, Cal. &apos;28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. &apos;28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. &apos;28 Benwell, Oswald F Hold Mags. &apos;28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. &apos;28 Blumenthal, Hugo 44 Pine St., New York, N. Y. &apos;28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. &apos;28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. &apos;28 Brown, Colvin B Chamber of Commerce, Washington, D. C. &apos;28 Burt, Maxwell Struthers Southern Pines, N. C. &apos;28

Jan 1, 1934

Albin, B. R Billings, Mont. Amster, Nathan L 25 Broad St., New York, N. Y. Bache, Jules S 42 Broadway, New York, N. Y. Barrett, C. P6338 Harper Ave., Chicago, Ill. Baum, Frank G Hobart Bldg., San Francisco, Cal. Bayless, Hon. William S Russ Bldg., San Francisco, Cal. Bean, Louis H., V.P., Dwight P. Robinson & Co., Inc 125 E. 46th St., New York, N. Y. Beatty, Ross J 1106 First National Bank Bldg., Chicago, Ill. Benwell, Oswald F 205 Colorado National Bank, Denver, Colo. Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. Bingham, Charles W 1542 Hanna Bldg., Cleveland, Ohio. Blumenthal, Hugo 44 Pine St., New York, N. Y. Boettcher, Charles Ideal Cement Bldg., Denver, Colo. Bowlus, Thomas H Iola, Kans. Bragg, E. B Carmel, Cal.

Jan 1, 1929

Albin, B. R Billings, Mont. &apos;28 Amster, Nathan L 25 Broad St., New York, N. Y. &apos;28 Bache, Jules S 42 Broadway, New York, N. Y. &apos;28 Barrett, C. P 5338 Harper Ave., Chicago, 111. &apos;28 Bayless, William S Russ Bldg., San Francisco, Cal. &apos;28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. &apos;28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. &apos;28 Benwell, Oswald F Hold Mags. &apos;28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. &apos;28 Blumenthal, Hugo 44 Pine St., New York, N. Y. &apos;28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. &apos;28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. &apos;28 Brown, Colvin B Chamber of Commerce, Washington, D. C. &apos;28 Burt, Maxwell Struthers Southern Pines, N. C. &apos;28

Jan 1, 1936

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman EDGAR RICHARD, Vice-Chairman D M LIDDELL Secretary, 7 Wall St.. New York. N. Y. C. A. BORN, Treasurer JOHN V. N. DORR LEWIS W. FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman JAMES G. CARLETON. Vice-Chairman E. E. BUGBEE Secretary-Treasurer, Mass. Inst. of Technology, Cambridge, Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman OSCAR LACHMUND, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON S. SHEDD

Jan 12, 1917

By John J. Gilman

F many years it has been suspected that a correlation existed between pits produced by etching and the density of dislocations in crystals. In 1953, the interest in this correlation was greatly stimulated when Vogel et al&apos; demonstrated a 1:l correlation between etch pits and dislocations in low angle grain boundaries of germanium. About two years ago, the author began attempts to produce etch pits at dislocation sites in zinc mono-crystals. These attempts met with success a year or so ago,&apos; and since that time a survey has been made of the etch pit patterns that are associated with various modes of deformation in zinc monocrystals. Unfortunately, the etching technique that will be described is too delicate for use as an accurate quantitative tool. Nevertheless, it has been of considerable assistance in clarifying the structure of plastically deformed crystals. Technique Many attempts were made to produce etch pits in high purity zinc crystals. It was found that several techniques would produce surface grooves at grain boundaries that had misorientation angles greater than about l°, but no technique was successful for boundaries with smaller angles. Among the things that were tried were: electrolytic CrO, (both etching and polishing concentrations), HNO, in various water and alcohol solutions, dilute HC1, many 0-0,-Na,SO, solutions, Cr0,-HC1 solutions, picral, electrolytic Na,S,O,, and electrolytic NaOH and KOH. A few attempts to use cathodic sputtering and thermal etching were also made.

Jan 1, 1957

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per &apos;C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons&apos; interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3&apos; All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.&apos;s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.&apos;s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By F. Lowell Lawrance

JOHN SMITH, citizen of the U.S.A., has become so accustomed to reading that Congress has appropriated billions of dollars to pay war costs. that he no longer is impressed by relatively small figures, such as several hundred thousand or a few million, in connection with Government departments.

Jan 1, 1944

By FRABK HERVEY PETTINGELL

THE stock exchange and its functions is about as well understood by the average individual as the fourth dimension. What is a stock exchange? Divested of the rules and regulations by which it is governed, and the facilities it provides for the convenient handling of securities, it would be in its nude state nothing more or less than a meeting place for brokers. The stock exchange in America dates back to 1752, when a group of merchants of New York established a meeting place at the foot of Broad Street for the purpose of dealing in meal and slaves. The first definite orgarization, however, had its beginning in 1792 when 24 New York brokers signed an agreement not to buy or sell public stock for less than one quarter per cent. commission. From this small group has grown by gradual degrees, the greatest organized security market in the world, namely, the New York Stock Exchange. At the present time there are 27 stock exchanges in the United States and 5 in Canada. Based on the volume of business transacted, the Los Angeles Stock Exchange ranks 6th among them. This is attributable to the fact that strictly speaking Los Angeles has never been a stock exchange town, like some other large cities. Take for instance San Francisco, which supported one stock exchange from 1862 to .1882 and has since supported two. No city, by the way, should tolerate two stock exchanges at the same time. It is an economic folly and a senseless duplication that can be compared with rival telephone companies or competing street railway systems, paralleling each other&apos;s lines and always leads to trouble and confusion, and sooner or later one or the other falls by the wayside. While Los Angeles has had stock exchanges of one kind or another since 1896, none of them attracted much attention until 1899 when the present exchange was organized and it did not get well under way until along in 1906.

Jan 1, 1925

By Charles W. Dickson

Jan 1, 1904

By R. C. Mahon

During the early history of the Lake Superior district, tamarack timber was used almost exclusively in the wines. It had the strength and lasting qualities necessary for a satisfactory mining timber. But about fifteen years ago the tamarack trees were attacked by a blight which killed nearly all of them so today no tamarack timber is available. Hemlock, spruce, and poplar have neither the necessary strength nor the lasting qualities for mining timber, but a large supply of maple and birch is available. These have ample strength but, when placed underground, fail by decay in about three years. This means that, instead of replacing the timber sets once in fifteen years, it must be done five or more times in the same space of time which involves not only incraesed timber costs but more important, an increased labor cost.

Jan 1, 1949

By T. N. Rhodin

There can be two types of films on solids, those which are stable in mono-layers and those which tend to aggregate into three dimensional structures. A great number of metal films formed by condensation onto a solid base are unstable in the sense that they will aggregate into crystals providing the atoms possess sufficient surface mobility. The crystalline structure of the film is strongly influenced by the base in many systems and, in some cases, a single orientation prevails when the force fields around the atoms in the supporting crystal are sufficiently strong.&apos; Relatively little is available in the literature about the nature of these forces and the role they play in promoting a preferred orientation of the atoms arriving at the substrate surface. An understanding of their periodicity and magnitude relative to the surface forces characteristic of the film itself should provide insight into the critical dependence of film orientation on the nature and temperature of the substrate. In addition, this effect may be very useful in preparing samples for surface studies. The study of the physical and chemical characteristics of pure metal surfaces has been severely handicapped by the presence of strongly adherent foreign films. Furthermore, the randomness of the surface orientation has obscured interpretation of experimental results. Evaporation of metals in high vacuum onto carefully selected substrates under ideal conditions for preferred orientation appears suited to the preparation of flat, oxide-free, oriented films for surface reaction studies. Many factors influence their structure and some understanding of the mechanism of their formation is a necessary prerequisite for obtaining satisfactory surfaces for study. The dominant factors in defining film structure are film thickness and growth rate and the nature, condition, and temperature of the substrate. GENERAL ASSEMBLY The system was enclosed in an 18 in. bell jar which rested on an L-shaped neoprene gasket on a ground steel plate as indicated in Fig 1. Rapid evacuation of the system to 10-6 mm mercury was facilitated by a 4 in. manifold, 2 in. packless valve, and an extra large diffusion pump. Suitable arrangement of valves on a secondary manifold readily permitted introduction of purified gases

Jan 1, 1950

By AIME AIME

THE John Fritz Gold Medal for 1929 was presented to Herbert Hoover at the Executive Mansion on April 25, at a luncheon given by Mr. Hoover to present and past members of the Board of Award, preceding medalists, and presidents and secretaries of the American societies of Civil, Mining and Metallurgical, Mechanical, and Electrical Engineers. The presentation party of forty engineers which gathered at the White House, from all parts of the United States, was made up of past presidents of the four senior national engineering societies that established the John Fritz Medal and included five men who had received the medal in previous years. These former medalists were Edward Dean Adams, J. J. Carty, J. Waldo Smith, Elmer A. Sperry and Ambrose Swasey. This medal is the highest honor bestowed by these four national engineering societies, having a membership of 60,000. It is awarded not oftener than annually for "notable scientific or industrial achievement, without restriction on account of nationality or sex." In accordance with custom, the award to Mr. Hoover was made tentatively and without announcement in October, 1927, and was formally con- firmed and announced one year later.

Jan 1, 1929

By Frederick T. Williams

THE purpose of this paper is to discuss the relative merits of the large 31/8 in. machine and the small 21/4-in. tappett machine in driving development-headings ; and although the . data here presented were obtained from cross-cut headings alone, experience has shown that the results are equally true in drifting, raising and winning. Recently we drove two parallel cross-cuts through the same formation, using a 3k-in. machine at the breast of one cross-cut., and a 2k-in. machine of the same make at the breast of the other. The results of this work afforded an ideal comparison, since in both cases the headings were advanced through rock practically of the same hardness and breaking-properties ; the amount of sludging was equal, and there was no difference in the condition of the steel or the machines, in the air-pressure or in the experience of the operating-crews. Some operators in the Cripple Creek district contend that there is ground which cannot be handled with the small machine, the holes being too small to contain enough powder to pull the ground, etc. The results obtained in working the property of the Portland Gold Mining Co., however, show that the ground worked by them does not fall in this class. During a period of two years there have been driven, with the small machine, 4 miles and 308 ft. of development-headings, through a diversity of ground, including Pike&apos;s Peak granite (a coarsely porphyritic type of granite), highly indurated, andesitic or phonolytic breccia, true massive andesite, trachytic phonolyte, tuffas, and along dikes of decomposed basalt and hard phonolyte; in every instance a satisfactory record was made. The headings here described were driven through highly indurated, andesitic breccia, having a hardness of from 5.2 to 7.2

Mar 1, 1906

[ ] DISCUSSION F A LORIA*-The method of testing gun steel for resistance to surface cracking described in this paper was restricted to the examination of small, rod-shaped specimens The writer would like to point out the importance of other factors in producing defects in forged and bored gun tubes which would not be apparent in this investigation because of the nature of )he test Actual section size would accentuate the possibility of internal wall (bore) defects arising from unequal expansion between the internal and external wall surfaces on firing, resulting in internal tearing Checks and tears on the inside walls arise from internal tensions and nonuniformity on cooling, but the internal tearing can be reduced by using alloys of low expansion and of good thermal conductivity so as to reduce the difference between the outer and inner wall surfaces Also, the possibility of the location of inclusion segregates within a machined gun tube becomes more likely than in a small test specimen The effect of these nonmetallics on gun life and performance is evident when one realizes that the inclusions are soft yet brittle They reduce the amount of plastic deformation which can take place before cohesive failure occurs Once localized fracture has occurred at the position of a chain of these inclusions, a sharp notch (crack) is formed which produces stress conditions more favorable to cohesive failure than to plastic deformation These cracks aid erosion by providing channelways for the explosive gases, eventually leading to the tearing out or spalling of blocks of metal Oxidation of the surface may be partly responsible for the change in the surface of gun steel during firing observed by the author The appearance of burn on the surface is an indication that high temperatures were reached on firing, resulting in a slight oxidation of the surface Since the color of the oxidized film depends on both temperature and time, a higher temperature is required for a given color to form when it is caused by explosive heat, which acts for only an extremely short time at a given spot, than when it is caused by ordinary tempering The cross section of the gun steel specimen, Fig 16, illustrates that the repeated firing temperatures were high enough to cause

Jan 1, 1948

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,&apos; as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900&apos; . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900&apos; until a vacuum of 10&apos;5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

By L. S. Darken

It has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernstl in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and FuossZ with results which have recently been confirmed experimentally by Harned and Nuttall. This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author,4,5 who pointed out4 that "for a system of more than two components it.is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepti- cism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley" in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion of acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 10500 C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1949