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By S. Tiwary, S. Samanta, B. N. Pandey, N. C. Saxena, R. Sinha, B. P. Nandy, B. Singh

Subsidence investigations over one bord and pillar and one longwall caved panel at Dhemomain colliery showed that, although the width-depth ratio (0.82 and 0.83) and working and strata conditions were almost identical, the maximum subsidence over bord and pillar panel was 46.2 per cent of extraction thickness against only 6.9 per cent over longwall panel. The angle of draw was 13O to 210 and 66 to 95 per cent of the subsidence had taken place immediately after extraction. The subsidence profiles were not symmetrical and were of funnel like shape. There was wide variation in subsidence movements over caved faces in India mainly due to difference in the composition of supercumbent strata.

Jan 1, 1983

By E. T. Turkdogan, P. Grieveson

It is shown experimentally that, by making use of the coupled S-O reaction in ionic melts, it is possible to transfer slclJur or oxygen from a lozv to a high chemical potential through an ionic nzenzbrane. This uphill transfer of sulfur is accompanied by a counter downhill transfer of oxygen and vice versa. The Materials balance shows that the amoulits of sul -fur and oxygen lost or gained by one system are the same as those gained or lost by the other systenz — the two systejns being separated by an iofzic membmne. The systems used in these experi?nents were solid Mn-MnS-Mno and liquid Fe-S-0. Sufficient results were obtained Lo study the kinetics of the transfer and the indications are that the counter diffusion of sulfide and oxide iojzs in the membrane is the rate controlling process. WHEN an ionic oxide-melt reacts with an atmosphere containing sulfur and oxygen-bear ing gases the following reaction occurs: 1/2 S2 (gas) +O2- (melt) = S2- (melt) + 1/2 0, (gas) [1] Under the restrictions that i) electric conductance in the melt is purely ionic and ii) each constituent element in the melt does not change valence, the solution of an atom of sulfur in the melt will result in the evolution of an atom of oxygen, so that the electric neutrality is maintained. For a given temperature and melt composition, the equilibrium concentration of sulfur in the melt is determined by the ratio, po2 /ps2 , in the gas phase and not by the individual partial pressures of oxygen and sulfur. This has been demonstrated by a number of investigators, for example by Richardson and withers', Fincham and Richardson,la by St Pierre and Chipman,' and by Turkdogan and Darken.3 In his Howe Memorial Lecture for 1961, Darken discussed the possibility of uphill pumping of sulfur through an ionic membrane at the expense of oxygen. TO test the validity of this concept associated with coupled reactions, experiments were carried out in the following manner. A presintered mixture of Mn-MnS-MnO and prefused mixture of Fe-S-0, contained in platinum and iridium crucibles, respectively, and separated by a thin layer of soda-glass (to act as an ionic membrane), were placed side by side in an evacuated silica capsule and sealed. This was then kept at 1400°K for a required time to allow Reaction [11 to occur via the ionic membrane. When partial equilibrium is reached, the ratios Po2 /pS2, for systems on either side of the membrane, are equal and the flux of sulfur and oxygen through the membrane becomes zero, although the individual partial pressures po2 andp,, in these two systems may differ considerably.

Jan 1, 1962

By Francis H. Brownell

During the 1920's lead consumption in the United States reached the highest average total ever known. For the ten-year period 1921-'30, it was slightly over 600,000 tons per year, or say 50,000 tons per month, and the price averaged 6.81 per lb. But the I930's witnessed a severe drop in the consumption of lead is in other business activities. The average U.S. consumption for the ten-year period 1930-'40 was slightly less than 380,000 tons per year, or under 32,000 per month, with the average price dropping to 1.191c. per lb. The outlook in early 1939 was for a continuation of this average consumption and price a demand of 35,000 to 40,000 tons per month, and a price level of 4 1/2 to 5c. in the United States.

Jan 1, 1941

By G. W. Mao, A. M. Gaudin, D. W. Fuerstenau

Activation of sphalerite with copper salts has long been thought of as a chemical reaction of the following form: ZnS + Cu++ [=] CuS + Zn++ [ 1 ] Early experimentation1-3 showed that the reaction seemed to be stopped by the coating of insoluble copper sulfide, but since the analytical methods were crude, it was only surmised that the reaction could proceed by diffusion. Probably the most conclusive evidence for reaction (Eq. 1) was obtained by Cooke,4 who found a stoichiometric replacement of Zn++ by Cu" after 50 days' reaction at about 100°C. Cooke also found the sphalerite to be covered with a rather thick coating of covellite, which in¬dicates that activation is a continuing replacement of Zn++ by Cu" rather than diffusion of Cu" throughout the sphalerite lattice. However, the occurrence of diffusion at high temperatures has been observed.5,6

Jan 4, 1959

BOSTON SECTION R. L. AGASSIZ, Chairman, - JAMES G. CARLETON, Vice-Chairman, E. E. BUGBEE, Sec.-Treas., Mass. Inst. of Technology, Cambridge, Mass. W. E. C. EUSTIS, G. A. PACKARD. The forty-fifth meeting of the Boston Section was held, at the Engineers' Club, on Tuesday, Nov. 6, 1917. Mr. F. C. Carstarphen, tramway engineer of the American Steel and Wire Co., was the guest of the evening. After dinner, Mr. Carstarphen gave a most interesting illustrated talk on the subject of aerial tramways. The views-showed the various forms of aerial tramways and three' unique installations, one carrying 285 tons of coal an hour, undoubtedly the maximum quantity transported by any tramway up to this time. The second installation is that of a lumber-carrying tramway, 5 miles long, operating in California. The last views illustrated a 13 ½ -mile tramway for carrying salt over the

Jan 2, 1918

By AIME AIME

MEMBERS of the Engineering Education Committee held two meetings at Joplin preliminary to the opening of the main meeting there. The first was held on Sunday afternoon. It was attended by all who had arrived early enough and as among the dozen or' fifteen who were present the heads of a half dozen schools of mines were included it was a representative gathering. C: H. Fulton, chairman of the Committee presided and T. T. Read acted as secretary of the meeting. The chair., man reminded those present that last year there had been some discussion as to the advisability of the proposal, made by Edward Steidle, that a, separate society, devoted to education in the mineral industry, he organized. Many .people had felt that there are already so many societies in existence to demand one's time and attention, that it would be a mistake to add to their number and the counter suggestion had been made that the work of this committee could be so reorganized as to meet all the needs that a separate society could fill. He therefore presented for discussion these four' questions: (1) Shall a subcommittee .be appointed to study, and report in February, 1932, the possibility of the reorganization of the work of the Engineering Education Committee into the equivalent of an' Institute division; (2) if the work is so reorganized what shall be the relation of the work of the Committee (division) to the work of the-Society for the Promotion of Engineering Education; (3.): what are the, cardinal objectives of education for the mineral industry; and (4) what should be done as regards the movement in some institutions to plan their work-in the light of that being done in other institutions, for example, in geophysics?

Jan 1, 1931

By Sheldon P. Wimpfen, Ralph H. Sweefser

FOR centuries the pumping of water has been one of the chief problems to be overcome by the persistent men who win the mineral wealth of the world. Profitable operations have often been forced to suspend activities as the mine penetrated well below the water table or when sudden rushes of water were encountered. To operate below the local water level requires continuous pumping equal in volume to the amount of water flow¬ing into the mine workings. Often the water to be removed exceeds the tonnage of valuable material produced. To be above local water level is a valuable asset. Modern mining practice permits nothing short of the extraction of the last pound of profitable ore from a mineral deposit. In the days before the development of mechanical and electrical power as we know it today. water in any quantity was a major

Jan 1, 1948

By Arthur C. Spencer

(Glen Summit Meeting, June, 1911.) THREE great deposits of iron-ore, in Camaguey and Oriente Provinces, Cuba, are well known to me through careful field-examinations executed in the years 1901 and 1907. In 1901 I visited the Cubitas iron-ore district, which lies about 12 miles distant from the city of Camaguey in a northerly direction, and the Mayari district, which includes the Sierra Nipe, lying opposite Nipe bay on the north side of Oriente Province. In 1907 I again visited the Cubitas district, and also made a sojourn of several days in the Moa district, where the extensive deposits of iron-ore were observed and studied. The observations of 1901 were made under the auspices of the then Military Governor of Cuba; Gen. Leonard Wood, and my conclusions concerning the value of these deposits were incorporated in a report.1 The examination of certain denouncements of iron-ore in the Moa district in 1907 was made in behalf of iron-masters operating in the United States, to whom I reported the existence of large amounts of easily-workable limonitic iron-ore, properly designated " brown iron-ore " in the terminology now current among iron-ore producers in the United States. In 1908 I published a paper entitled Three Deposits of Iron Ore in Cuba, outlining the occurrence and origin of the surficial ores existing in the Cubitas, Mayari, and Moa districts.2 . 1 A Geological Reconnoissance of Cuba, by C. Willard Hayes, T. Wayland Vaughan and Arthur C. Spencer, printed as a part of the report of the Military Governor of Cuba for the year 1901, vol. i. 2 Bulletin No. 390, U. S. Geological Survey, pp. 318 to 329 (1908).

Mar 1, 1911

By AIME AIME

IT IS impossible in this short sketch to give a detailed description of each part of the plant at Bethlehem, therefore, only such facts will be touched on as are necessary to give a general idea of the works. The extent of the plant, and the fact that the units making up the various departments are located in different parts of the works, make it impracticable to mention the departments in any regular order with regard to their location. They are, therefore, mentioned approximately in the order of their relation to each other with reference to their functions in the making of the various products.

Jan 1, 1924

By J. M. Roberts, N. Brown

The stress-strain behavior of zinc single crystals was measured over a strain range of 10-6 to 10-2. The phenomenon of macroyielding was observed in detail and plastic strains were detected at almost zero-stress. Closed hysteresis loops were observed during loading and unloading in the strain region of about 10-5. From the hysteresis a frictional stress on the dislocation of about 6 psi was obtained. A preliminary analysis indicates that impurities are primarily responsible for the friction. Nonelastic Strains as much as 10 -4 were recovered depending on the amount of prior deformation. Part of the recovered strain occurs instantaneously upon unloading and the remainder occurs at zero stress. The time dependence of the recovered strain was measured. THIS investigation is concerned with the details of plastic deformation preceding the ordinary yield point as measured with the usual strain sensitivity of about 10-4. The approach leads to internal friction observations in the hitherto neglected frequency range below 10-1 cycles per sec. It is believed that if the phenomenon of macroscopic yielding is to be understood, then the stress-strain curve in the neighborhood of the macroyield point should be greatly magnified. It may then be possible to determine whether macroscopic yielding is a unique event or whether it is a process which begins gradually at a lower stress. In the case of low-carbon steel a unique event obviously occurs at the macroscopic yield point as indicated by a drop in the load, but copper appears to exhibit a gradual transition from the elastic to the plastic state. In zinc the yield point is rather abrupt although the data indicates that some plastic deformation precedes large scale yielding.' One of the purposes of this investigation is to determine whether there is an abrupt transition from the preyield microstrain region to the region of macroscopic deformation. Such a rapid transition would support the concept that there is a critical stress for yielding. The concept that yielding is a unique event associated with such phenomenon as activating a Frank-Read source, freeing the dislocation from solute atoms, dislocations cutting through dislocations, or dislocations moving freely by one another, has been expounded widely on theoretical grounds. It is hoped that highly sensitive measurements of strain in the neighborhood of the macroscopic yield point will shed some light on the event known as the "Yield Point". EXPERIMENTAL METHOD 1) Specimens—High-purity zinc was cast into spherical graphite moulds in air and grown into spherical single crystals by the Bridgman method under a positive pressure of Argon gas. Spectro-graphic analysis of cleaved sections from four crystals showed a purity of 99.994 pet Zn. The specimens were acid machined with an 1/8 in. gage section in a form similar to those used by Parker and co-workers.2 Bausch type grips were fastened to the specimen by Epon VI adhesive. The specimens were oriented so that only [1120] (0001) slip occurred. Fig. 1 shows two of the specimens in the grips. Prior to each test, the gage section of the specimen was given a concentrated HNO3 chemical polish followed by alcohol rinsing and air blast drying. 2) Test Method- The shear tests were performed on an Instron testing machine and the experimental set-up was made very "hard". Strain could be measured to a sensitivity of 10 -6 by means of a capacitance gage extensometer. The design and calibration of this type of extensometer to measure microstrain, as applied to pure shear and tensile tests of metals, will be the subject of a separate paper—therefore, only a brief account will be presented here. The method essentially consists of attaching a

Jan 1, 1961

By F. Keller

SOME PHRASEMAKER has aptly said that nature made aluminum light but research made it strong. Research has been a vital element in the past progress of the aluminum industry and its future growth likewise depends upon the application of the results of research. The role of aluminum products in World War II is well known and this metal will certainly be increasingly important in the postwar world. Some of the principal developments in the war years were in the field of high-strength aluminum alloys. New and stronger alloys were developed which enabled designers to get increased speed and performance in our fighter planes and bombers. The aircraft industry will continue to use these new materials for peacetime passenger and cargo airplanes. High-strength alloys will also find structural applications in trucks, buses, trains, ships, and bridges.

Jan 1, 1946

By Herbert Hoover

THERE is one problem of the new administration that has received the attention and thought of the organized engineers of America for many years past. This is the problem of the reorganization of the Federal Government. The, inadequacy, the wastefulness, and the inefficiency of our federal organization was evident, enough under pre-war conditions. These inadequacies, these inefficiencies, these wastes were exhibited to the country during the war at the cost of millions. Congress has placed the problem in the hands of a very able Congressional Joint Committee, but if this Joint Committee succeeds in securing the imminently necessary results it will only be by full insistent support to it by public opinion. Many attempts have been made at reorganization before but all, of them have gone to the same crematory-the interminable differences in opinion among the executive and legislative officials over details.

Jan 1, 1921

By Thomas T., Read

IN this survey of the progressive development (of education for the mineral industries throughout the United States, the review of .the history of each school has usually been completed wherever it is first mentioned, but the history of the schools in the cities of the eastern seaboard was not carried beyond 1870. It is necessary now to cover what happened during the period of approximately the last quarter of the nineteenth century in several of the schools in the east. Philadelphia Of Philadelphia, it has been related in chapter 4 that the Polytechnic College of Pennsylvania began offering a curriculum leading to the B.S. in mining in 1853; that the school did not prosper, and finally closed about 1890. The establishment of a Department of Mining, Arts, and Manufactures at the University of Pennsylvania in 1855-56 was also mentioned, but its history was not carried beyond 1860. In 1859 J. Peter Lesley was appointed professor of mining in the University of Pennsylvania. The son of a cabinetmaker, born in Philadelphia Sept. 17, 1819, he had taken his A.B. degree at the University of Pennsylvania in 1838 and then secured a position on the Geological Survey of Pennsylvania under H. D. Rogers. When the Survey was discontinued, in 1841, he went to Princeton to study theology, was ordained a Presbyterian minister and followed that career until 1852, when the Pennsylvania, Geological Survey was again started and he rejoined its staff. He published "A Manual of Coal and its Topography" in 1856, and studied at the École des Mines, Paris, in 1856-57. He published an 800-page "Iron Manufactures Guide" the year that he was appointed to the staff at the University of Pennsylvania. In 1863-64 a College of Agriculture, Mines, Arts and the Mechanic Arts was established, but it was not a separate school

Jan 1, 1941

RECEIPTS [Magazine Advertising $ 62,564.83 Magazine Sales 3,591.44 Totalm 66,156.27 Dues, Arrears7,032.88 Dues. Current96,839.74 Dues, New Members6,525.00 Dues, in advance 1,907.02 Initiation Fees7,584.00. Sale of Transactions3,909.03 Sale of Binding7,845.05 Sale of Special Editions 338.20 Sale of Year Book76.20 Sale of Pamphlets1,189.06 Sale of Authors' Reprints867.54 Miscellaneous Receipts62.93 Interest on Bank Balances1,712.89 Interest on General Reserve Fund337.50 Interest on Life Membership Fund557.84 Interest on James Douglas Library Fund....5,491.89 Total Receipts$208,433.04] [ ]

Jan 1, 1925

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

Receipts General Funds: Initiation fees : $ 4,705.00 Arrears of dues :...: 1,345.79 Current dues 40,924.78 Advanced dues 1,613.29 Sale of binding 10,367.48 Sale of advertising.: :... 7,109.98 Sale of transactions 4,085.42 Sale of special editions : 553.17 Sale of bulletins and pamphlets 2,028.22 Miscellaneous Receipts: Returned to general funds from land fund account 146.50 Interest on investments and deposits ; 353.29 Sale of pins and fobs 278.05 Library insurance cancelled..: 103.95 Sale of library books 28.70 Refund .from Madison Affl. Student Society....11.22 Miscellaneous 396.47 $74,081.31 Cash balance December 31, 1914: 6,316.90

Jan 2, 1916

Magazine Advertising $ 62,564 83 Magazine Sales 3,591 44 Total 66,156 27 Dues, Arrears 7,032 88 Dues, Current 96,839 74 Dues, New Members 6,525 00 Dues, in advance 1,907 02 Initiation Fees 7,584 00 Sale of Transactions 3,909 03 Sale of Binding .. 7,845 05 Sale of Special Editions 338 20 Sale of Year Book 76 20 Sale of Pamphlets 1,189 06 Sale of Authors' Reprints 867 54 Miscellaneous Receipts 62 93 Interest on Bank Balances 1,712 89 Interest on General Reserve Fund 337 50 Interest on Life Membership Fund 557 84 Interest on James Douglas Library Fund 5,491 89 Total Receipts $208,433 04

Jan 1, 1923

By F. D. Rosi, C. H. Mathews

THE plastic properties of face-centered cubic metals below room temperature present a field of investigation which has not been extensively ex-plored. The work by Schmid and Boas1 has demonstrated the importance of temperature upon such properties as strain hardening and critical resolved shear stress. The work by Yamaguchi2 upon the shear stress as related to the number of slip bands accentuates the necessity for further experiments of a similar nature. The approach to a mechanical equation of state from the standpoint of thermal fluctuations and activation energies by Becker3 and more recently by Kauzmann4 further emphasizes the need for a quantitative and more comprehensive analysis of the dependence of fundamental plastic properties on temperature. The purpose of the present work was to investigate specifically: (1) The gross shape of the stress-strain curves at several temperatures, (2) the change in the critical shear stress as a function of temperature, and (3) the number and appearance of slip bands as a function of strain and temperature. Preparation of Specimens Single-crystal specimens of 99.996+ pct alumi-num, 1/2 in. in diam and 5 to 6 in. in length, were made by the Bridgman method of gradual solidification from the liquid state. The crystallographic orientation of the single crystals was determined from back-reflection, Laue X-ray photograms ac-cording to the method described by Greninger.6 In most specimens the Laue photograms showed double diffraction spots indicative of the lineage structure type of imperfection, discussed in great detail by Buerger.7 The angular spread of these spots was never observed to exceed 2". Most of the crystals were radiographed to insure against microporosity. In preparing the metal surface for optical microscopy, the following sequence of operations gave good results: The as-cast crystals were turned down in a lathe, 0.001 in. per cut, to obtain a 2.5 in. gauge length. The cold-worked layer resulting from this operation was removed chemically by etching with Tucker's reagent. Then the specimen was polished mechanically through 2/0 metallographic emery paper, after which it was etched again to remove the cold-worked layer resulting from the mechanical treatment. A 48-hr anneal at 580°C ±10°C followed so as to insure an essentially stress-free single crystal. After the annealing treatment, the specimen was electrolytically polished in a 2:l solution of methyl alcohol and concentrated nitric acid. With a current density of 10 amp per sq dm (decimeter) the time required to obtain a satisfactory surface varied from 10 to 12 min. The polish-ing was carried out for short periods of 2 min to avoid rapid deterioration of the solution as well as to enable the rotation of the specimen 180" for uniformity of polish. It was necessary to place the solution in a bath of dry ice in view of its explosive nature at room temperature. Etching of the electrolytically polished surface was accomplished by using the fuming etch-pit method recommended by Lacombe and Beaujard8 for high-purity aluminum. Method for Tensile Testing A modification of the loading equipment devised by Miller9 was used. In this apparatus, the specimen was suspended from a chain and gimbal arrangement (for axial loading) in a heavy steel framework connected at the bottom to a balanced 6:1 lever and bucket system. Loading of the specimen was accomplished by allowing sand to flow from a reservoir into the bucket suspended from the longer end of the lever-arm at a rate of approximately 3 lb per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire, strain gauge and an SR-4 portable strain indicator (type K), which permits a reading accuracy of 2 microinches per inch. For low-temperature study, the gauge was calibrated by measuring the elastic modulus of an annealed stainless steel rod, which is known to be independent of temperature."

Jan 1, 1951

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.' The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969