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By S. E. Maddigan, B. R. Zimmerman

MOST metallurgists are well acquainted with the contributions already made to the study of metals by the use of X-rays. On the one hand, the radiographic method is constantly becoming of increasing importance as a nondestructive testing procedure, while on the other hand the techniques of X-ray diffraction have made important contributions to the fundamental knowledge in studies of phase diagrams, stress conditions, and so forth. A new, and as yet insufficiently appreciated, tool exists in the application of microradiography to alloy structures. This new procedure in many respects bears the same relation to microscopic investigations as does macroradiography to the gross inspection of metal surfaces. However, where macroradiography is used ordinarily to determine the soundness of the metal structure, this new method can be used not only to investigate micro-un- soundness but also to examine the distribution of the constituent elements within the body of the alloy. When combined with the normal procedures of microscopy, this offers a technique of great potential power. It is intended in this paper to present a few examples of copper-base alloys demonstrating the additional knowledge obtained from the microradiographic method. The detection of micro-unsoundness is demonstrated in Fig. I for a sample of cartridge brass as cast. The sample appeared quite sound when viewed under the microscope, but in reality was thickly populated with minute voids. This application of the method conforms in every way to conventional large-scale radiography and has been used to facilitate production of metal for vacuum devices.1 The true potentialities of the technique are revealed by comparison of Figs. 2a and 2b, which are respectively a- photomicrograph and a microradiograph of a cast alloy of 80 per cent Cu, 10 per cent Sn, 10 per cent Pb. The remarkable difference in appearance provides some concept of the additional information this method may yield when used as an auxiliary to microscopic studies. Fig. 2a shows two phases of the copper-tin system plus segregated lumps of lead. Fig. ab, on the other hand, shows with exceptional clarity the actual dendritic growth of the metal crystals during solidification. The practice of microradiography depends upon the laws of absorption of X-rays. This subject has been reviewed thoroughly in recent papers,1,2,3 but for clarity a brief resumé will be given here. As is well known, when a beam of X-rays is transmitted through a layer of homogeneous material, the intensity is reduced according to the relation:[ ]

Jan 1, 1944

The annual meeting of the Woman's Auxiliary was held on February 19, at 10 a. m. The president, Mrs. Sidney Jennings, said in her greeting "it is a matter of congratulation that during the past year when the demands upon women for work of all kinds has been so large our membership has grown from the 50 enrolled at the first meeting a year ago to over 300 today. Some women, when. asked to join the organization, say that they are doing so much work in other ways that they have no time for work in a new organization, but the director for Canada struck the right note in her report when she told us of the splendid work the wives of mining engineers are doing in Canada, as individuals and as leaders and members of various organizations doing patriotic work. We do not want to divert such women from the work they are now doing, but we do want them to enroll as members of the Woman's Auxiliary and let us know what they are doing, that they play give inspiration to others." Reports were made by the directors of the following sections: Canada, Chicago, Colorado, Columbia, New York, Puget Sound and St. Louis, in some of which sections excellent progress has been made in food conservation, foreign war relief, including the adoption of fatherless French children, and in work for our own engineering regiments. These reports were read, accepted, and placed on file. The reports of the corresponding secretary, of the recording secretary, and of the treasurer, were read, accepted, and placed on file. Various amendments to the Constitution were proposed and accepted, and copies of the Constitution, as amended, will be mailed to all the members of the Woman's Auxiliary.

Jan 4, 1918

Sailing westward from the Society Islands in the fall of 1774, England's noted explorer Captain James Cook discovered New Caledonia-that long, linear island that has played such an important and varied role in the history of nickel. Upon his return to England the following year, Cook's announcement of this uncharted island generated governmental interest, but its distance from the Island Empire, the troubles in the colonies, and the difficulties with France combined to keep English interest indirect and in the background of the then-current events.

Jan 10, 1968

By Samuel Taylor

IT is customary for the president of an engineering society, in his annual address, to describe either some engineering problem with which he has beer connected or to review the work of the society during his administration. My first thought, this being the sesquicentennial year of our nation, was to review the advance in coal mining for the past fifty years, during which period I have been more or less intimately con-nected with the bituminous coal industry, and have personally witnessed most of the great changes which have occurred in methods and machinery used in the production of coal, but preparation of the requisite address would take more time than could be spared to prepare it, and its presentation would consume so much time that it .would not be suitable. The new arrangement providing for giving the presi-dent's address at the business meeting makes it more .appropriate to review the work of the Institute during the past year, together with some suggestions which appeal to me as being of advantage to the future wel-fare of the Institute, which I will try to do briefly. The work of the business office has been reviewed in the Secretary's report and it will not be necessary for me to dwell on it. Suffice it to say, it seems to be going along very well. Additional work could be done which would be to the advantage of the Institute, if we had the money with which to defray the necessary ex-pense incident to it, but I will refer to this again later. I would be derelict if I did not refer to the splendid work of the Secretary and the Assistant Secretary. Keeping in touch with all the sections, which number now about 26, and affiliated student societies which number 40, besides special committees, and represent-ing the Institute on various boards, provides work enough to occupy the Secretary's time almost exclu-sively. In addition to this the Secretary and the As-sistant Secretary have the work of editing and publishing the TRANSACTIONS of the Institute; the issuing of the magazine, MINING AND METALLURGY, in the splendid manner in which it goes out to the mem-bership is no light task and I think they should receive the commendation of the membership for this work.

Jan 3, 1927

By Carlton D. Hulin

ARE we a "have" or a "have-not" nation in our domestic supply of metals and minerals? Impinging on the ears of a people weary of war and faced with the problems of reconversion to peace, the import of this question has built up with the momentum of an avalanche. Stemming from statistics cited by Pehrson and accelerated by the pessimistic and possibly biased statements of Ickes, hardly an issue of any technical periodical dealing with mining has appeared during the past year but within whose pages was to be found some comment, some discussion of the question: Are we a "have" or a "have-not" nation? We have proved commercial reserves of high-grade iron ore in the Lake Superior region sufficient for 22 years, based upon the prewar rate of consumption; commercial copper reserves to last only 34 years, one fourth being inferred ore; zinc sufficient for nineteen years, over half being inferred; lead for twelve years, two thirds of which is inferred; mercury for only three years. So read the figures. Although admitting that these figures may be extended by new discoveries, by the use of marginal and submarginal ore, and by further technological advances, are we nevertheless to assume complete pessimism in the acceptance of the meaning of these statistics; are we to expect a rapidly increasing dependence upon foreign sources of mineral supply; are we to believe that we are at or near the peak of the "metal age" as has been held by Theodore J. Hoover? Or is some more optimistic viewpoint possible?

Jan 1, 1947

By J. S. Owens, R. W. Marsden, J. W. Emanuelson, R. F. Werner, N. E. Walker

The iron ores of the Mesabi Range occur in a 340 to 750-foot thick, Precambrian cherty iron formation termed "taconite." For about 65 years, extensive natural iron ore bodies were mined, and the ores either shipped as a direct ore or processed by gravity methods to a shipping grade iron ore. Since 1956, magnetite taconite ores, occurring in magnetite-rich horizons in the Biwabik iron formation, have been commercially concentrated and agglomerated. The transition from natural ores to concentrating-grade ores is progressing rapidly so that, in the near future, a major percentage of the iron ore shipped from the Mesabi Range will be as iron ore pellets produced from taconite. Natural iron ores of the Mesabi Range occur in the Biwabik formation as trough ore bodies in elongated channels and as irregular and tabular deposits in fractured areas associated with faults and folds. Ore bodies range in size from a few thousand tons to hundreds of millions of tons and may occur in any part of the iron formation. In some areas of strong ore development, ore was formed from the hanging-wall argillite to the footwall quartzite. The natural ores and beneficiating-grade natural crude ores were formed by the oxidation of the iron minerals, magnetite, greenalite, stilpnomelane, minnesotaite, and siderite, to hematite and goethite and by the removal of much of the silica in the cherty quartz and in the associated silicates by leaching. The ores are believed to have formed by the oxidizing and leaching action of surface waters. Magnetite taconite ores occur as stratigraphic zones in the Biwabik formation where it contains sufficient magnetite to be concentrated profitably, by magnetic methods, to give a magnetite concentrate that is agglomerated into a high quality product. Unoxidized taconite has an extensive distribution away from and between channels of oxidation and leaching but only a part of the unoxidized taconite is of ore grade. Two general types of magnetite taconite ore occur: ( 1) magnetite taconite of the Main Mesabi Range, generally west of Mesaba, which is composed of magnetite associated with cherty quartz, greenalite, stilpnomelane, minnesotaite, and carbonates and (2) magnetite taconite of the Eastern Mesabi, generally east of Mesaba, composed of magnetite associated with quartz, cummingtonite, actinolite, ferrohypersthene, hedenbergite, fayalite, hornblende, pyroxene, garnet, and biotite. The Mesabi taconite is a metasediment derived from an iron- and silica-rich chemical sediment that has been regionally metamorphosed and, on the eastern end, additionally metamorphosed by the Duluth Gabbro Complex.

Jan 1, 1968

By M. C. LAKE

THE industrial development of the United States has been stimulated by the presence of high-grade iron ore in the Lake Superior district. These great deposits have been susceptible to economical extraction and are conveniently located for cheap lake vessel transportation to the great consuming centers. The district furnishes from 80 to 85 per cent of the iron ore annually consumed in the United States, and a full understanding of the available supply of this great commodity is so important that it is well to consider whether or not the industrial supremacy and national independence attained as a result of the abundance of cheap ore are permanent. The enormous deposits of high-grade ore available in the Lake Superior district have been the foundation upon which the vast industrial structure of the steel and allied industries has been built. It is extremely important to the country as a whole, and especially to those States and communities now dependent on Lake Superior ore for their prosperity, that their industries shall retain the particular advantages with which they are now endowed, and that a generous supply of high-grade raw material be available for their consumption at a satisfactory cost. The steel industry is so basic and fundamental that any fluctuation in the cost of its finished products as determined by the supply and cost of the raw materials involved in its manufacture will necessarily affect the business of a wide variety of industries which are dependent on it.

Jan 1, 1926

By P. Barnes

The sums given in the accompanying table are those actually paid for material and labor up to about August, 1875; but, as some parts of the machinery were not wholly completed at the starting of the works in September, 1875, the statement cannot be taken as an absolutely correct note of the total cost. A complete description, with engravings of the building and machinery, was given in Engineering, April 26th, 1878, in a paper by Messrs. A. L. Holley and Lenox Smith, to which convenient reference may be made. A detailed list of the construction accounts has been given in a paper, by the present writer, in vol. vi, Transactions of the Institute. A summary is given in the table of the items in each class which enter into the total cost, and also a note of the proportion which each of these items forms of the whole. A concise view may thus he obtained of the facts embodied in the statement as a whole, even though it cannot lay claim to completeness in showing the entire or final cost. An urgent suggestion has reached the writer from a distant country that such statements of cost to be really most serviceable should give the details in days of labor, in weight of iron, and in number of brick, and to this an assent is most cordially yielded. It is true, however, that the mere labor of copying arid compiling these details to such a degree of minuteness, would be very great, and, in any event, the probable difference between the plans of an existing establishment and one projected, would be so wide as to render even so complete a statement of cost of little more real service than the approximate notes given herewith.

Jan 1, 1879

By P. Barnes

THE sums given in the accompanying table are those actually paid for material and labor up to about August, 1875; but, as some parts of the machinery were not wholly completed at the starting of the works in September, 1875, the statement cannot be taken as an absolutely correct note of the total cost. A complete description, with engravings of the building and machinery, was given in Engineering, April 26th, 1878, in a paper by Messrs. A. L. Holley and Lenox Smith, to which convenient reference may be made. A detailed list of the construction accounts has been given in a paper, by the present writer, in vol. vi, Transactions of the Institute. A summary is given in the table of the items in each class which enter into the total cost, and also a note of the proportion which each of these items forms of the whole. A concise view may thus be obtained of the facts embodied in the statement, as a whole, even though it cannot lay claim to completeness in showing the entire or final cost. An urgent suggestion has reached the writer from a distant country that such statements of cost to be really most serviceable should give the details in days of labor, in weight of iron, and in number of brick, and to this an assent is most cordially yielded. It is true, however, that the mere labor of copying and compiling these details to such a degree of minuteness, would be very great, and, in any event, the probable difference between the plans of an existing establishment and one projected, would be so wide as to render even so complete a statement of cost of little more real service than the approximate notes given herewith.

Jan 1, 1879

By John J. Cioston

THE steadily rising flood of gold production from all parts of the world has created an avalanche of rumors regarding the stability of the present price of this metal. Markets have been unsettled from Johannesburg to London from New York and Toronto to Melbourne, despite repeated denials from, American and British authorities of any immediate intention to alter the price. Various economists and financial writers have blossomed forth with predictions that the price would be set at the old level of $20.67 per oz.; some have even been so brash as to state That a price of $15 would be necessary to bring production within control. These effusions, based entirely upon monetary theories and with no regard to production costs, serve to confuse rather than clarify the situation.

Jan 1, 1937

By George S. Rice

GROUND movement and subsidence is an important matter from several points of view and it is regrettable that more papers have not been written on this subject in the past year. Damage may be done to surface buildings or to the higher workings of a mine, and a study of the subject gives valuable in- formation on hanging-wall or roof control. The latter objective is strikingly shown in a recent paper presented by Jack Spaulding on Oct. 21, 1937, before the Institution of Mining and Metallurgy, of Great Britain, entitled "Theory and Practice of Ground Control in the Kolar Gold Field, India." All may not agree with some of his theories that were deduced from studies of the many violent rock bursts at depths of 5000 to 7000 ft., but the data obtained are of great value. His theories of symmetrical ring stresses and symmetrical domes which are pictured as perfect are rather hard to understand as such uniformity is un- likely in view of the irregularities in the formation due to folds and fractures of various kinds. All will agree in principle with this idea of domal effects, which have been observed in many countries, but they are generally irregular.

Jan 1, 1938

By G. J. Ballmer

Drilling and blasting 12-in. blastholes started about the middle of 1946 and has worked out so well that about one half of the blasting, formerly done with 9-in. holes, is now done with 12-in. holes. In most of this work the harder benches were chosen for the 12-in. size because these were the areas where the greatest difficulty was encountered in thorough fragmentation. At the start of this experimental work a 42-T Bucyrus- Erie churn drill was available whereas all other blasthole drilling was being done with 29-T rigs. The large drill was first equipped with a standard 9-in. string of tools but it could not drill quite as fast as the 29-T drills. How- ever, when the weight of the string was increased about 700 lb, or to a total weight of about 3500 lb, it was found that the 42-T exceeded the drilling speed of the 29-T by about 25 per cent. When a 12-in. bit was substituted for the 9-in. bit the 42-T rig again dropped behind the drill- ing rate of the 29-T rigs. At this stage of the experiment the 42-T was using a 12-in. bit with detachable points and the total weight of the string of tools was about 3800 lb. It took longer to change the drill points than it did the regulation bit and this accounted for some of the slower drilling rate. When a heavier stem and standard construction 12-in. bits were used it was found that the 42-T could drill a 12-in. hole slightly faster than a 29-T could drill a 9-in. hole even in the hardest rock in the pit.

Jan 1, 1949

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By E. V. Daveler, Frank L. Antisell

CERTAIN physical and chemical properties of copper are so intimately related that a change in variation of the physical properties indicates a certain chemical change. The standard specifications of copper of the American Society for Testing Materials are based upon physical characteristics with one exception, namely, the copper contents. Certain phenomena of the surface indicate the adaptability of the metal for forging or rolling. The writer believes that it is much simpler to produce shapes that are metallurgically correct than those that are mechanically satisfactory. The appearance of the surface of the copper when cooled is considered as to its "pitch," or the general contour of the surface, and the "set," or the decail appearance of the surface of the shape. The set of the copper is, in a very large measure, directly related to the pitch; and so intimately are these characteristics connected that they are often used as synonymous terms by the refiner when he is speaking of well-refined copper. Oxygen is often spoken of as a medicine for copper, it being used to regulate the pitch.

Jan 1, 1920

By AIME AIME

IN ORDER to carry on its work most effectively, the Committee on Industrial Organization (now known as the Committee on Industrial Relations) consists, of .a number of sub-committees, each composed of a chairman and members who are especially fitted to carry out the work designated by its title. With only one or two exceptions, all of these committees made reports at the New York meeting of the Institute, in February of this year, abstracts of which follow.

Jan 1, 1920

By J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.&apos;-&apos; Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965

By Louis D. Huntoon

(New Haven Meeting, February, 1909.) THE Hammond Mining and Metallurgical Laboratory is the gift of Prof. John Hays Hammond to the Sheffield Scientific School of Yale University. Professor Hammond was graduated from this school in the class of 1876, and has always shown great interest in its welfare and progress. In 1903, he offered to build and equip for it a mining and metallurgical laboratory. This offer was gratefully accepted by the trustees; and in October of the same year the architect, W. Gedney Beatty, and the writer were employed to draw up plans for the building, which is the largest of its kind in this country. The Treasurer&apos;s report shows the total gift of Professor Hammond, including land, building, and equipment, to have been $128,741.53. This does not include $5,000 given by Professor Hammond to defray incidental expenses. The detailed cost of the machinery and installation, included in the above sum, is as follows: Machinery, $9,846.00 Pipe and fittings, 925.05 Hangers, shafting, pulleys, belts, etc., . 357.83 Steel-work, tanks, launders, etc., . 272.19 Screens for sizing ore, 411.37 Lumber, 1,896.36 General Supplies Hardware, . $135.96 Tools, 263.66 Paints, . 04.63 Electric and incidental, . 439.57 - 1,043.82 Machine-shop material, 259.44 Labor, 722.29 - 981.73

Mar 1, 1909

By J. V. Vogel

Jan 1, 1969

By P. R. Sahm, T. V. Pruss

Mixtures of fine GaSb and Gds as well as preal-loyed GaSbl,As, powders were hot-pressed at 690°C and 25,000 psi. Dense alloys with compositional gradients of less than 5 pct were obtained from mixtures containing about 20 mol pct GaAs. For x < 0.2, there were increasing compositional gradients, and for x > 0.2 a GaAs-rich second phase appeared in the microstructure. Densification as well as alloying wlechanisms were enhanced by dissociation and, possibly, oxidation reactions of the powders. Densification of coarse prealloyed material, however, primarily depended on plastic flow phenomena and required temperatures just below solidus and pressures of 50,000 psi Thermal and electrical properties were measured. Although in no case was the figure of merit of melt growth materials approached closer than to within 25 pct, the better overall thermoelectric properties were found in coarse-grained, prealloyed materzals which had been compacted to near theoretical density and where grain regrowth had been induced. Similar results are believed to hold in other binary 111-V compound systems if processed under similar conditions. The densification of unalloyed GaSb powders during pressure sintering (= hot pressing) was shown to depend strongly on powder particle size.&apos; Fine powders displayed a "liquid skin effect" that enhanced compaction through the presence of liquid gallium, whereas coarse powders compacted predominantly by plastic flow. The liquid skin effect, in particular, appeared attractive for alloying GaSb with other, higher-melting, III-V compounds, and to densify these in a one-step operation. This is of special interest in the case of III-V compound alloys as the conventional techniques of melt growth or long-time annealing of powders2 is very time-consuming, especially in cases where a large separation of liquidus and solidus can be expected, such as in GaSbl alloys.2 It was felt that experimentation with this system, a particularly unfavorable example, would allow us to extrapolate to several other, more favorable, cases. Uses of Ill-V alloys are most evident in thermoelectric energy conversion devices.&apos; For this reason certain thermal and electrical properties were measured and compared to those of melt-grown material and to hot-pressed prealloyed powders. EXPERIMENTAL PROCEDURE The pressure-sintering apparatus has been previously described.&apos; Using this equipment, both powder mixtures of GaSb with GaAs and prealloyed GaSbl-,As, powders were hot-pressed. The mixtures were pre- pared from cast GaSb and melt-grown GaAs. The prealloyed material was obtained from stoichiometric melts, initially heated to 1200°C in an evacuated quartz ampoule, and then annealed in the solidus-liquidus interval. A typical annealing cycle consisted of a heating to 850°C (1 hr), extended successive annealing at 750°C (65 hr), and slow stepwise cooling (25 hr) to below solidus. The GaSb, GaAs, and GaSbl-,As, materials were ground in a vibrational mill to particle sizes below 500 . A jet mill reduced these further where necessary. Fine powders were analyzed by Coulter counting for their size distribution. Average sizes by volume were calculated from the data. Mixing of the powders, where necessary, was carried out through rapid vibrational motion. The hot-pressing operation consisted of a degassing period of 15 hr, in most cases at 690°C, followed by several hours of compression, normally 25,000 psi at 690°C for powder mixtures and 50,000 psi at 710°C for prealloyed powders. The chemical compositions were confirmed by X-ray fluorescence analysis. To estimate the degree of solid solution achieved, lattice parameters were determined and interpreted according to Vegard&apos;s rule. In addition, optical microscopy helped to correlate the relative amounts of the phases present as well as the degree of porosity to the measured density. To reveal grain boundaries, polished surfaces were etched4 with H 2 O:H 2 O:HCl = 2:l:l. In several cases microscopic concentration gradients were monitored by electron-probe analysis-. RESULTS AND DISCUSSION Alloying and Densification of GaSn-GaAs Powder Mixtures. After preliminary experiments showed that no appreciable alloying took place in mixtures of coarse GaSb (22.5 p) and fine GaAs (2.5 p) powders, hot pressing of mixtures was confined to fine powders only (3.1 and 2.4 p, respectively). Alloying and densification apparently occurred simultaneously with a grain regrowth mechanism which depended on the presence of a liquid phase.&apos; The liquid phase was provided by the dissociation of GasbS particles into liquid gallium and antimony above 555°C. This not only enhanced grain regrowth and densification, as in unalloyed GaSb,&apos; but took on additional importance here for the alloying process. Alloying was speeded up by the resulting liquid-solid interaction as compared to the very slow solid-state diffusion process normally expected at these temperatures.&apos; The results obtained with a series of powder mixtures have been compiled in Table I. It is seen that for mixtures with less than 20 mol pct GaAs, x < 0.2, the compositional ranges increased and for x > 0.2 a GaAs-rich phase and free antimony appeared in the microstructure in sizable amounts.

Jan 1, 1968

By Frank Foote, E. R. Jette

In recent years the constitution of the high-silver aluminum-silver alloys has been extensively investigated. Hansenl has reviewed the literature to 1935. More recently, Obinata and Hagiya,2 Hofmann and Volk,3 Taziri4 and Tishchenko5 have confirmed the general features of the phase diagram in the region around 25 atomic per cent aluminum. In this paper we present the results of high-precision measurements of lattice constants of the silver-rich alpha solid solution in the homogeneous range and the neighboring two-phase regions. These results are used to establish the nature of the solid solution, the identity of directly measured densities with those calculated from lattice constants and the homogeneity limits of the alpha solid solution with respect to three different neighboring phases. A study of the earlier investigations indicated that the last two subjects in particular required new and accurate data. Experimental Procedure Preparation of the Alloys.—The alloys were made from high-purity silver and aluminum. The silver was "Proof Silver," 99.999 per cent pure, supplied by the U. S. Metals Refining Co. The aluminum was 99.97 per cent pure (contained Si, 0.009 per cent; Fe, 0.0016 per cent; Cu, 0.004 per cent) and was supplied by the Aluminum Company of America. The lattice constants of these two materials have been reported by Jette and Foote.6 Weighed amounts of the two metals were placed in alundum crucibles and melted in vacuo in a high-frequency induction furnace. The melts were allowed to cool in the crucible, the ingots thus obtained weighed about 10 grams. These ingots were then filed clean, hamered, again cleaned and given a homogenizing anneal in vacuo of from 6 to 15 days at temperatures ranging from 500" to 695°C. The ingots were air-cooled from the annealing temperature. Lattice-constant Measurements.—Carefully prepared filings for X-ray analysis were sealed into evacuated quartz or Pyrex tubes and annealed for various periods of time at suitable temperatures. The furnaces used were vertical, rapid-quenching furnaces, the samples being quenched by crushing the sample tube under water by means of a heavy plunger. The general X-ray technique has been previously described6 The cameras were of the symmetrical, back-reflection, focussing type. Ka, radiation from a cobait-nickel alloy target was used. The wave-length values were taken from the second edition of Siegbaum&apos;s book.7 A correction for the index of refraction was applied and the lattice constants were calculated by the method of Cohen.8, 6 The lattice constants were calculated to a common temperature of 25°C., using the value of the linear expansion coefficient of pure silver as 18.9 X 10-6. Presumably the expansion coefficient for

Jan 1, 1941