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By Arthur Knapp

The practical application of mud-laden fluids in wells has been the subject of many papers.' However, there seems to have been little investigation of what actually happens when mud-laden fluids are applied to a loose porous sand. The assumption is that the fluids penetrate the sands and that there is some plastering action. The degree of penetration and the relation of plastering action to wall stability is not generally known. This paper describes a series of experiments made in an attempt to observe, in laboratory apparatus, the action of mud-laden fluids under conditions simulating those to be found in a well. For the purposes of this discussion all fluids containing solid matter in suspension are mud-laden fluids. Series I: Penetration of the Pores of Uncemented Sands The subject of the penetration of porous formations by water is discussed in detail in Water-Supply Paper No. 67 of the U. S. Geological Survey. No attempt was made to repeat the experiments described therein. The results of the first experiment of this series are given simply to show the capacity of the apparatus used. The conditions in this first experiment were maintained throughout the remainder of this and the second series, except where noted. The experiments of Mills, McCoy, and others on subsurface flows, adjustments, migrations, etc., deal with the oil, water or gas within the porous beds.V he experiments described herein deal with the conditions immediately surrounding the bore hole.

Jan 1, 1923

By F. F. Sharpless

ON Saturday evening, Sept. 9, a small party of Institute members, their wives and friends, left New York to attend the Fall Meeting of the Institute at San Francisco. In this party there were: President and Mrs. Arthur S. Dwight; Mr. and Mrs. George D. Barron; Mr. and Mrs. H. J. Stehli; N. S. Spencer and Miss Spencer; the Secretary and Mrs. F. F. Sharpless. They were joined at Chicago by E. F. Eurich, and by Mr. and Mrs. R. L. Baldwin and daughter. Our party was met at Chicago by Mr. and Mrs. L. V. Rice, Mr. and Mrs. A. D. Terrell and W. F. Boericke, who constituted themselves an impromptu entertainment committee and proceeded to carry out a delightful little program. We were taken to the Lake Shore drive, where a stiff wind off the lake refreshed us after a sultry day on the train, and on our return to the city saw Chicago illuminated with all its brilliance of electricity. We were entertained at dinner at the Drake Hotel. In spite of being two hours late getting into Omaha, we were right on the dot at Denver on Tuesday morn-ing. Horace F. Lunt came to the hotel soon after breakfast, and told us that a trip to the mountains had been planned. Having learned the number in the party, he began to gather up his automobiles for a 10 o'clock start.

Jan 10, 1922

Geological and Natural History Survey of Minnesota, Minneapolis, Minn W. H Emmons, Director A list of publications will be sent upon application Orders for publications should be addressed to The University of Minnesota Press, Minneapolis, Minnesota The Geological Survey of Minnesota has a record of long and useful service Some of the papers published have been outstanding in their field A series of 24 Annual Reports, covering the years 1872 to 1895-98, inclusive, was issued, of which 16 are still available at a price. More important however, are the six volumes of Final Reports, in which is collected the material presented in the earlier Annual Reports. All the strictly geological papers are found in four of the volumes of the Final Reports. vol 1 (1872-1882), principally geology by counties, 2 (1882-1885), same as 1, 4 (1896-1898), same as 1, 5 (1898-1900), Structural and petrographic geology Prices for each volume, leather $3, cloth $2 50, excluding postage, unless other directions accompany the order, volumes of the Final Reports will be sent express collect. A series of Bulletins has been issued, of which a few are out of print. Considering only those available, and of greatest interest, they are: Bulletin 5, Natural gas in Minnesota, by N H Winchell (1889), 50 cents, 6, Iron ores in Minnesota, their geology, discovery, development, qualities and origin, by N H Winchell and H V.

Jan 1, 1933

M. AlbERtson, Chairman. Production Engineer, Shell Petroleum Corporation, Houston, Texas. R. P. McLaughlin, Associate Chairman. General Manager, Burnham Exploration Co., Los Angeles, Calif. Eugene A. Stephenson, Secretary-Treasurer. Professor of Petroleum Engineermg, Missouri School of Mines and Metallurgy, Rolla, Mo. Ezecutive Commillee M. Albertson, Chairman. C. E. Beecher, Empire Oil & Refining Co., Bartlesville, Okla. L. L. Foley, Petroleum Engineer and Geologist, Tulsa, Okla. R. B. Kelly, Division Manager, Pure Oil Co., Fort Worth, Texas. Hallan N. Marsh, Production Engineer, General Petroleum Corporation of California, Los Angeles, Calif. R. E. Somers, Geologist, The Gulf Companies, Pittsburgh, Pa. Production Engineering T. V. Moore, Vice-chairman. Charge Production Research Division, Technical Service and Development Dept., Humble Oil & Refining Co., Houston, Texas. Joseph Chalmers. De Bataafsche Pet. Maatschappij, The Hague, Netherlands. M. L. Haider, Petroleum Engineer, Carter Oil Co., Tulsa, Okla. Emile HUGUENIN, Deputy State Oil and Gas Supervisor, Los Angeles, Calif. Carl E. Reistle, Jr., Petroleum Engineering Dept. Humble Oil & Refining CO., Houston. Texas. Produclion J. Terry DUCE, Vice-chairman. Geologist, The Texas Company, New York, N. Y. Basil B. Zavoico, Associate Vice-chairman. Consulting Geologist, Houston, Texas. Engineering Research R. L. Huntington, Vice-chairman. Associate Professor, Petroleum Engineering, University of Oklahoma, Norman Okla. Economics Sidney A. Swensrud, Vice-chairman. Assistant to the President, Standard Oil CO., Cleveland, Ohio. Refinery Engineering Walter Miller, Vice-chairman. Vice-president, Continental Oil Co., Ponca City, Okla.

Jan 1, 1937

(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 L. L. Hirsch, W. M. Parris, P. D. Frost

IT has been established that titanium alloys con- taining sufficient amounts of ß-stabilizing elements, such as iron, chromium, or manganese, can be age hardened.' Adenstedt, Pequignot, and Raymer2 showed that age hardening occurred in a Ti-15 pct V alloy at room temperature after it was quenched from a temperature in the ß-phase region. During a recent investigation of the heat-treating characteristics of binary Ti-Mn and Ti-Cr alloys at Battelle, further evidence of low temperature aging was found. Appreciable hardening occurred in some of these alloys at aging temperatures as low as 212 OF (100oC). Indeed, the brief heating period employed for mounting metallographic specimens in bakelite resulted in hardening. It was felt that further information on this low temperature aging phenomenon would be of general interest in view of the large amount of work currently being done on titanium alloys. The alloys examined in this investigation were arc-melted in a water-cooled copper crucible as 3/4-lb ingots. Du Pont Process A sponge was used as a base material. The arc-melted ingots were forged at 1700" to 1800°F (927" to 982°C) and hot rolled at 1450°F (788°C) to 14 gage (0.064 in.) sheet. Small specimens were heated in argon at 1742°F (950°C) for 30 min and quenched in various liquid media or air cooled. They were then mounted in a room-temperature-setting resin and given a metallographic

Jan 1, 1954

The following is an incomplete list of members and guests who called at Institute headquarters during the period June 10, 1919, to July 10, 1919. Anvil A. Anderson, Rapid City, S. D. Roy N. McBride, U. S. Army. R. Hay Anderson, Mexico City, Mex. R. S. McIntyre, Berkeley, Calif. W. A. Barnes, San Francisco, Calif. H. R. Maier, Brooklyn, N. Y. Bennett R. Bates, Denver, Colo. Wm. D. Mainwaring, Philadelphia, Pa. Harlan H. Bradt, Duluth, Minn. Wm. E. Milligan, Chrome, N. J. H. Brings, San Francisco, Calif. Willard S. Morse, Tacoma, Wash. Robert S. Burg, Ocean Park, Calif. Arthur Notman, Bisbee, Ariz. D. W. Butner, Congo Belge, Africa. P. Nugue, Chalon Sr. Saone, France. George A. Camphuis, El Paso, Tex. George A. Packard, Boston, Mass. Fred Canan, Denver, Colo. C. L. Petzel, New York City. Walter H. Coleman, Prescott, Ariz. V. Porreaud, Paris, France. Fred Crabtree, Pittsburgh, Pa. Fred S. Porter, Seattle, Wash. Ross E. Douglas, Rancagua, Chile. R. W. Prouty, Morenci, Ariz. F. A. Downes, Golden, Colo. Charles E. Prior, Brooklyn, N. Y. W. G. Eberhardt, Tucson, Ariz. Louis Ravicz, Minneapolis, Minn. Charles H. Fulton, Cleveland, Ohio. Wm. Reed, El Oro, Mexico. Wm. R. Grunow, New York City. E. J. Ristedt, Globe, Ariz. Orr R. Hamilton, Lansing, Mich. A. M. Rodgers, Middletown, N. Y. T. N. Havlin, St. Louis, Mo. J. C. Scoles, Salt Lake City, Utah. G. M. Henderson, Weston, Mass. C. E. Siebenthal, Washington, D. C.

Jan 8, 1919

By E. Ackerman, L. Y. Tu, S. C. Sun

The use of ultrasonics in forming emulsions is not new. As early as 1927 Wood and Loomis' reported preparation of emulsions with ultrasonics. In 1935 Rschevkin and Ostrawskyz described the use of great ultrasonic power in producing fine emulsions of various oils and paraffin in water. Recently Oyama and Tanakahmployed ultra-emulsification to increase the effectiveness of sodium ethyl xanthate in flotation of chalcopyrite and galena. An emulsion is a two-phase system consisting of two incompletely miscible liquids, the one being dispersed as finite droplets in the other. The dispersed liquid is known as the internal or discontinuous phase, and the surrounding liquid is termed the external or continuous phase. There are two types of emulsions; one is oil-in-water (O/W) and the other water-in-oil (W/O). The word oil refers to the liquid other than water. Circumstances exist in which the emulsion type is not clearly defined, and the internal and external phases both contain portions of the opposite phase. This is said to be a dual emulsion. Among the many hypotheses', 6v proposed for the formation of emulsions, the Bancroft's adsorbed film or double interfacial tension theory is widely accepted. Bancroft ""educed that in the process of emulsification the interfacial tension between oil and water is lowered by the formation of an emulsifying film, which contains the adsorbed molecules and/or ions from the emulsifying agent and the two liquids.

Jul 1, 1955

By A. G. Raine

For the technological age in which we live, with the constant goal of further improvement in the efficiency of mechanized systems, the need for a replacement of the antiquated drill and blast method of shaft construction has been recognized. For over a decade now; the trend in shaft construction has been toward large diameter bored shafts using either raise boring methods or more flexible, rodless "down the hole" boring machine. The limits of conventional shaft sinking have been reached, the mining regulations are more stringent, and the environmental agencies more aggressive, all contributing to the growing need for development of the rodless shaft boring machine. In the last three years in the United States, world shaft construction records have been achieved using a V-Mole machine, designed by Mirth GmbH of West Germany, using American electrics and hydraulics. Shafts of 7.0 meters (23 feet) diameter, totaling 2,255 meters (7,400 feet) in depth have been constructed at high advance rates, yet with unusually low accident rates. Bearing in mind the high cost of today's mining labor and the inherent danger associated with conventional shaft sinking, this alternative method of shaft construction achieves a fast, competitive, low manpower requirement, whilst enhancing a safer environment for the labor force. Recent results have proven that program time savings of 50 percent over conventional shaft sinking can be achieved which can be directly translated into improved client cash flow projections and more accurate project budgeting.

Jan 1, 1984

The resolution drafted by J. W. Richards, J. V. N. Dorr, and Allen H. Rogers on the death of J. E. Johnson, Jr., and adopted by the Board of Directors, is as follows: "The Boards of Directors of the American Institute of Mining and Metallurgical Engineers wishes to place on record its great personal loss in the sudden death of Mr. J. E. Johnson, Jr., our fellow Director of the activities of the Institute, a member our Executive Committee, Chairman of the Institute's Committee on Admissions, and Vice-chairman of its Iron and Steel Committee. "A mere recital of these positions of trust and responsibility, which he filled with conscientious efficiency and marked ability, shows how greatly the Institute has lost by his death. No one else of the Institute's officers could have been so illy spared. We, his colleagues, take up his tasks with a sense of our inability to discharge them as well as he, and this with a doubled sense of our loss. "Others have written and spoken of the blow which his death has been to the furtherance of the metallurgy of iron and steel. His pre-eminence in this line is one of the facts of which the Institute is justly proud. Here his personality, originality, courageousness in advocating new principles, clearness of writing and forcible presentation of facts, are irreplaceable. His two great treatises on the blast furnace are his literary and scientific memorial.

Jan 7, 1919

Meeting of Dec. 19, 1913.-The President reported the appointment of the Committee on Junior Members and Affiliated Student Societies, and the Committee on Coal and Coke, which .appointments were approved. The President was authorized to appoint the members of a Committee on Safety and Sanitation. The President appointed the Finance Committee of the Institute as a Committee to audit the accounts of the Treasurer (By-Law V). On the recommendation of the Executive Committee, Charles F. Rand was appointed a representative of this Institute on the Board of Trustees of the United Engineering Society for a term of three years (By-Law XIV of the Institute, By-Law XI of the U.E.S.). The Executive Committee reported that it had passed the following resolutions: That the next summer meeting of the Institute be held at Salt. Lake City during Aug. 10 to 14, 1914, inclusive; That an exchange of .the Bulletin and Transactions be made with the Canadian Bureau of Mines; That a sum of $50 be contributed for the year 1914 to the Commission publishing the Annual Tables of Physical and Chemical Constants; That the Secretary be given power to reduce at his discretion the number of exchanges between the Bulletin and other publications which are not retained as a permanent part of the Library; That the contract for binding Volume XLV of the Transactions be awarded to the Butler, Ward Co., in accordance with their bid of Nov. 21, 1913;

Jan 1, 1914

By Charles E. Wait

In the use of the apparatus purchased for the new chemical laboratories of the university, no piece has given us more satisfaction, or has been a greater success, than a new still which is the subject of this paper. In the designing of this still I had two definite objects in view ; one, the utilizing of steam from the large 60 horse-power boiler used in heating the building, and the other, a provision for making distilled water with gas, when steam from the heating-plant was not available. The still is encased in wrought-iron, with a lining of asbestos, and is provided with a float which automatically regulates the flow of water from the supply-pipe. It was made for me by G. J. M?rrle, Pforzheim, Germany, and was imported by Messrs. Eimer & Amend, of New York City. It is a beautiful piece of apparatus, and the workmanship is excellent in every detail. The essential parts of this apparatus will be understood by consulting the accompanying figures, but a few words of explanation may be appropriate. The still has a capacity of seven gallons, and is made of heavy copper, tin-lined. It has a water-gauge showing the height of the water in the still, also an exit for steam, and safetyvalve, V; inlet for steam through a coiled perforated block-tin pipe; also an outlet, 0, for cleaning out the still; and there is also a heavy

Jan 1, 1895

(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 Institute headquarters during the period August 1, 1916 to September 10, 1916: C. L. Cantley, New Glasgow, N. S. H. M. La Follette, La Follette, Tenn. D. A. Cowell, Columbus, Ohio. Montrose L. Lee, Montevideo, Uruguay. Alexander Deussen, Houston, Texas. V. H. McNutt, Billings, Mont. Chas. E. Dutton, Goldfield, Nev. J. W. Maller, New York, N. Y. H. S. Emlaw, Grand Haven, Mich. Edwin W. Mills, Tul. Mi Chung, Chosen, J. M. Gillette, Swatsburg, N. Y. Korea. E. Gorilla, San Antonio, Texas. Francis R. Pine, Elizabeth N. J. Bertram Grant, Kingman, Arizona. Frank A. Ray, Columbus, Ohio. Ruger W. Hay, Bisbee, Arizona. John A. Rice, El Paso, Texas. C. F. Hendricks, Cobalt, Ontario. W. E. Rice, Ringwood Manor, N. J. Stanley C. Herold, San Jose, Cal. W. H. Staver, Lynchburg, Va. Lloyd Hoffman, Pottersville, N. J. Ralph H. Sweetser, Easton, Pa. Charles Hunter, London, England. Kirby Thomas, New York, N. Y. G. Jansen, Benkoelen, Sumatra. Henry Traphagen, Union Hill. T. H. Jenks, Oatman, Arizona. M. M. Valerius, Tulsa, Okla. Warren jenny, Chanaral, Chile. Wilfrid B. Wainewright, London, Eng. Walter A. Barrows, Jr., of Brainerd, Minn., has been elected president and general manager of the Thomas Iron Co., Easton, Pa., to succeed Ralph H. Sweetser, whose resignation of several months ago becomes

Jan 10, 1916

The following is an incomplete list of members and guests who called at Institute headquarters `during the period Aug. 10, 1918 to Sept. 10, 1918. Amil A. Anderson, Hill City, S. D. A. A. Holland. H. G. S: Anderson, Hurley, N. Al. Paul S. King, Wilmington, Del. Louis A. Barton, Capt., Engineers, U. S. A. Herbert G. Officer, Washington, D. C. K. Baumgarten, lst Lieut., U. S. R. A. B. Parsons. Charles W. Boise, Belgian Congo. Robert R. Pollock, San Francisco, Cal. Henry C. Carlisle, The Pas, Manitoba. Frank A. Smith, Edgewood, Md. J. Ross Corbin, Boyertown, Pa. Edward C. Thompson, Kennett, Cal. S. Le Fevre, Forest Glen, N. V. Malcolm M. Thompson, Morsemere, N. J. Harold P. Ford, Cleveland, 0. Lester C. Uren, Berkeley, Cal. William L. Hogg, Waynesboro, Va. Harold W. Aldrich has been appointed assistant general superintendent of the Inspiration Consolidated Copper Co. at Inspiration, Ariz. Capt. Percy E. Barbour, formerly with the New York State Troopers, has been granted a leave of absence from the Department for the period of the war, by the Governor, and has been appointed Captain in the Engineer Corps, U. S. A. He served on the Mexican border in the New York State National Guard. A. C. Barke, formerly with the United States Smelting, Refining and Mining Exploration Co., has accepted a position with the United States Fuel Co. at' Salt Lake City, Utah.

Jan 10, 1918

Karl L. Fetters moves to the front of the AIME organization this month as the 1964 President of the Institute. He will take the chair vacated by outgoing President Roger V. Pierce at the Annual Meeting in New York, already well-rehearsed in his forthcoming duties after a year of preparation as AIME President-Elect. Dr. Fetters is highly qualified for his new responsibilities on both the administrative and professional level. For the past five years, he has been vice president for research and development at The Youngstown Sheet and Tube Co. in Ohio, where he has achieved wide recognition as an out- standing metallurgist and executive. A native of Alliance, Ohio, he obtained his early education in the public schools of his home town and displayed a singular precocity when he launched his professional career as a chemist for the Morgan Engineering Co. at the age of 16. His new career, however, was soon set aside in favor of four years of higher education at the Carnegie Institute of Technology, whence he emerged in 1931 with a bachelor's degree in metallurgical engineering. Surprisingly, and perhaps owing to the employment stringencies of the Depression years, the first job his new qualifications earned him was that of stationary engineer at the Cunningham Sanitarium in Cleveland. After two years of ministering to the mechanical ailments of this institution, Dr. Fetters relinquished his post for a more suitable one in the field of metallurgy.

Jan 2, 1964

By Robert W. Zimmerman

POROUS SOLID COMPRESSIBILITIES There are four different compressibilities associated with porous solids, each relating the fractional change in either bulk volume or pore volume with the change in either pore pressure or confining pressure. These will be referred to as Cbc, Cbp, Cpc, and Cpp, with the first subscript denoting the relevant volume, and the second subscript denoting the relevant pressure. They are defined as: [ ] Note that minus signs are included in two of the definitions so that each of the compressibilities will always have a positive value. In general, each compressibility depends on the elastic moduli of the matrix material, the porosity, and the exact geometry of the pores. Taking the latter factor into account calls for separate analysis for each different pore shape, which of course can only be attempted for a few relatively simple cases. But lower bounds for each of the four compressibilities can be found, independant of pore structure, in terms of only the porosity (0) and the elastic moduli of the matrix material (any pair chosen from K, E, G and V). The first step is to find relationships between the four compressibilities, starting with the following observation: If a porous solid made of a linear elastic, isotropic and homogeneous matrix material is subjected to uniform hydrostatic pressure of magnitude P on its external and all of its internal (pore) surfaces, the state of stress in the solid will be exactly the same as that which would occur

Jan 1, 1982

By D. C. Buffum, L. D. Jaffee

THAT the path of brittle fracture in temper brit-tle steel differs from the path in unembrittled steel has been known for some years1 More recently it has been recognized that alloy steels, at least, display two forms of temper brittleness1 which may be called upper-nose and lower-nose. No experimental evidence has been published, however, to show that the two forms can be distinguished by simple inspection of brittle fractures. Fig. 1 is a photograph of the fractured surface of a V-notch Charpy specimen of SAE 3140 steel in which temper brittleness developed during heat treatment in the lower-nose temperature range.' The steel was austenitized 1 hr at 900°, tempered 1 hr at 675", and embrittled 48 hr at 500°C, with water-quenching after each treatment. The temperature of transition from ductile to brittle fracture in the Charpy test was + 2°C (criterion of transition: 100 pet fibrous). The hardness was Re 25; the austenite grain size ASTM 8. This specimen was broken at 150°C in the standard Charpy test and absorbed 6.6 ft-lb; its fracture was rated 0 pet fibrous. Fig. 1 shows that the fracture appeared rough to the naked eye. At the side of the specimen away from the notch (the side which was in compression during the test), the surface as a whole deviated sharply from a plane. At higher magnification, X60, the surface gave

Jan 1, 1959

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET's and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.' More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET's. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET's with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By G. A. Chadwick, D. Jaffrey

The morpho1ogies and orientation relationships of the phases in the Sn-Zn and A1-A13Ni eutectic systems were examined by electron microscopy and X-ray diffraction techniques. In each alloy the "transition" from the lamellar to the fibrous morphology was found to be one of scale, not of type. The minor phase in both systems exhibited certain well developed facets which were not affected by changes in the ingot solidification rate. The crystallographic relationships displayed by the pairs of phases in both systems were also insensitive to the growth rate. In the Sn-Zn alloy, the unique relationship of: growth direction - II [1201 Sn - II [01101 Zn and ribbon interface plane 11 (101) Sn 11 (7012) Zn was determined. The Al-Al3Ni alloy phases did not possess any particular orientation relationship, though the Al3Ni phase invariably grew in the [010] direction and exhibited the same set of facet planes. These results are discussed in relation to current eutectic growth theories and explanations of the "lamellar to fibrous transition". THE lamellar to fibrous transition that occurs in many eutectic alloys has been the subject of considerable speculation and experimental study. In some alloys it can be induced solely by an increase in the solidification rate,'-3 whereas in others the transition supposedly occurs only if the lamellae are forced to grow out of the overall ingot growth direction.4-6 he cause of this latter type of transition has been attributed to deviations of the lamellae from their low energy habit planes;4'5'7 fibers are produced because the sustaining force for lamellar growth (a low energy boundary) is destroyed. Implicit in these explanations is the assumption that fibers are circular in cross-section and completely lacking in low energy inter-phase interfaces. The "natural" growth rate dependent transition has been studied less thoroughly although Tiller8 has attempted a theoretical explanation of it. Tiller's arguments are not completely satisfactory9 but his suggestion that the relative undercoolings of the solid/liquid interface for lamellar and fibrous morphologies are growth rate dependent cannot be totally discounted; it is possible, for instance, that the relative interfacial undercoolings could alter and produce the observed morphology change if the orientation relationships between the phases and the associated interphase bound- ary energies were sensitive to growth rate. Salkind et al." have reported finding a change in the orientation relationships in the A1-A13Ni system accompanying the lamellar to fibrous transition, but contradictory evidence has also been reported for this3'" and another system,12 so the position remains unclear. In an attempt to clarify matters a study was made of the "lamellar to fibrous" transition in the Sn-Zn and A1-A13Ni eutectic systems; the morphologies of these two selected systems are quite similar when viewed by optical microscopy. In the present research the morphologies and morphology changes were investigated by electron microscopy. The orientation relationships existing between the eutectic phases were also determined for both morphologies in both eutectic systems. EXPERIMENTAL PROCEDURE The materials and method of alloy preparation and ingot solidification for the Sn-Zn system have been reported previously.2 In this investigation nine horizontally grown ingots of the highest purity (99.9997 pct) were used. The temperature gradient in the melt was not intentionally varied and was approximately 10°C per cm. Seven growth rates between 1.3 cm per hr and 20 cm per hr were imposed. The A1-A13Ni alloys were prepared from "Spec. Pure" nickel and 99.995 pct aluminum by melting the components in an open alumina crucible and casting the melt into the cold graphite mold. Six ingots of the Al-Al3Ni alloy were unidirectionally solidified at growth rates from 1 cm per hr to 12 cm per hr under high purity argon. A typical ingot was 20 cm long, 1 cm wide, and 0.75 cm to 1.5 cm thick. Samples taken from the bars at positions 12 cm from the nucleation end were examined by conventional orthogonal-section metallo-graphic techniques. When required, samples were mounted for X-ray diffraction analysis using the Laue back-reflection technique with a finely focussed X-ray source. The surfaces of the A1-A13Ni specimens were prepared by mechanically polishing them down to the 1 µ diamond pad stage followed by an electropolish in 80/20 methanol/perchloric acid solution at 0°C and 20 to 30 v. The Sn-Zn specimens were repeatedly polished on an alumina pad and etched in hot dilute (2 pct) nitric acid until the diffraction spots were found to be sharp. Thin films of the alloys were prepared for observation in an electron microscope by spark machining thin discs (0.03 to 0.04 in. thick) from longitudinal and lateral sections of the bars and elec-trolytically thinning them via a jet polishing technique. For the A1-A13Ni eutectic alloy, an 80/20 mixture of ethanol/perchloric acid at 40 v and 20°C was found to be satisfactory. A solution of 70/20/10 methanol/perchloric acid/butylcellosolve at 25 v and 20°C was used on the Sn-Zn alloy. For the former alloy the jet nozzles (cathodes) and the disc clamps were of aluminum;

Jan 1, 1970