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INTO their great Pacific Northwest counting house went the members of the Industrial Minerals Division recently, to count their blessings amidst the scenic grandeur and mineral wealth of the State of Washington. From their vantage point in Seattle, those who attended the IMD's fourth Pacific Northwest meeting turned their sights to the South and Southeast, scanned Montana, Idaho, Oregon and Utah, and predicted a very healthy economic future for their region. The praises of Idaho's booming phosphate industry were sung by Earl W. Murphy, secretary of that State's Chamber of Commerce. He said the establishment of Fort Hall, on the banks of the Snake River near Pocatello, first turned the eyes of the world toward what is now the center of the greatest known deposits of phosphate rock-the section adjacent to the common corners of Idaho, Wyoming and Utah. With the founding of Fort Hall, Mr. Murphy said, historians will also rank the construction of the first electric furnaces for the production of elemental phosphorous as equally significant in the commercial history of the West. Those furnaces were installed only last year by the Westvaco Chemical Div. of the Food Machinery & Chemical Corp. at Pocatello, at a cost of $8 million.

Jan 7, 1950

A discussion of the paper by Mr. Campbell, which was read by title at the Lake Superior meeting, but first presented at the New York meeting of the Iron and Steel Institute, October, 1904 (see p. 772). These papers are here published onder a mutual agreement between the Councils of the two Institutes, and will also be found in the Journal of the Iron and Steel Institute for the year 1901, vol. ii. Mr. William R. Webster, Philadelphia, Pa., said: We are under great obligation to Mr. Campbell for his exhaustive investigation, and the results he has put before us to-day. They are the most conlplete series of tests that have ever been made, where all the conditions of rolling, etc., were kept uniform. In discussing Mr. Campbell's first investigations, I claimed first, that the method of least squares, then used, would of necessity only gire the average value of any element, and that if the effect of any element was greater in the presence of high carbon than with low carbon this would not be shown by the method of least squares. Secondly, that the effect of manga nese should be considered on acid steel as well as on basic steel, instead of ignoring all the eff'ect of that element when it was below 0.60 per cent., as was then recommended by Mr. Campbell. I am pleased to note that the results of his present investigation confirm my views on these points. In presenting the results of his first investigation, Mr. Campbell referred to my investigation of 1893-94, and took exception to the value of phosphorus varying (depending on the amount of carbon present) from 800 to 1,500 lb. for each 0.01 per cent. He claimed that one might just as well consider the effect of phosphorus as being constant, and of carbon varying. I refer to this, as he now has introduced very similar conditions in his present tables, in that he gives variable values for manganese (depending on the amount of carbon present) for both acid and basic' steels. Can we now say, with more certainty than formerly, which element should be considered as haviup a constant effect ? There is one other point that I took up in my former discus-

Jan 1, 1905

Adams, John H., Pres. & Mgr., Alabama Lime & Stone Corpn., 1302-4-8 First Ave., Birmingham, Ala. '14 Adams, L. W., Otis Steel Co., Riverside Plant Cleveland, Ohio. '15 Adams, Leland D., Min. Engr., Mgr., Signal Mines Co., Goldbanks Quicksilver Co., 485 California St., San Francisco, Cal. '14 Adams, R. L., Min. Engr., Old Ben Coal Corpn., Mine 12 Christopher, III. `19 Adams, Robert M., Robert M. Adams Co 1201 Fidelity Bldg., Duluth, Minn. '20

Jan 1, 1925

By Courtenay de Kalb

REVISION of the United States mining law is needed. chiefly because of the following reasons: 1. The conceptions as to the characteristics of orebodies that were held at the time the statute of 1872 was enacted have since proved to be in many respects erroneous. 2. The operation of the existing law has been found to work unnecessary hardship upon many claimants to mineral land. 3. The existing statute fails in large degree to encourage development of mineral resources. 4. The existing law often produces conflict between placer and lode-claim rights, working unnecessary injustice to placer claimants. 5. The methods of establishing the rights of locators on United States mineral land are defective, and are not uniform throughout the States within which such lands exist. LAW OF THE APEX The objections to the so-called "law of the apex" are so well known as to require no detailed statement. It is sufficient to point out that the apex rule was based upon the notion that ore deposits consisted of well-formed veins included between definite walls, like the slice of ham in a sandwich. The fact is that veins conforming to that simple type are rare. Irregularity is the rule, and the chief metal production of the United States comes from masses which bear no resemblance to the tabular form of vein. Manifestly the law of the apex fails completely in such cases. Moreover, the tendency is constantly toward the exploitation of ores of lower grade than could formerly be worked, and such deposits exist mainly in the form of large irregular impregnated zones and masses, so that the future. development of our mineral resources would be continuously embarrassed by shadowy claims to extra-lateral rights by the locators of so-called apexes

Jan 2, 1915

By K. N. Weaver

In the early 1950's the cement industry began putting a new emphasis on geology. This article points up some of the industry's raw materials problems that geologists are uniquely qualified to handle. Portland cement can be made from relatively abundant industrial minerals and rocks, and this may explain why cement producers placed little emphasis on geology during the early days of the industry. After World War 11, however, the industry began to recognize the need for geological exploration and some of the larger companies began to build a permanent geological staff. This development has its roots in: 1) The rapid expansion of the industry. After World War II and continuing into the early 1950's the demand for cement far exceeded the production capacity. This placed a great deal of pressure on the producers to enlarge capacity at their plants and to develop new sites. 2) The closing of many cement plants due to inadequate raw materials. Producers feared lack of raw materials due to inadequate exploration and evaluation. 3) An ever increasing pressure for upgrading of the quality of portland cement, necessitated upgrading the quality of raw materials. 4) The increasingly large capital investment needed to build new cement plants required a higher degree of accuracy in reserve calculation. These reasons are more or less self explanatory and will not be elaborated on. They are outlined to illustrate the probable evolution of thought among cement management to justify the development of a geological staff. In the author's personal experience the geologist must continually readjust to changing conditions within the industry. For example, cement production capacity grew so rapidly that today production is only about 70% to 75% of rated capacity (73.8% in 1963). Therefore, whereas the geologist's function during the active expansion of capacity was primarily one of exploration, one of his major functions today is the development of existing reserves. This assumes of course that reserves at existing plants have been proven to be adequate in terms of the company's reserve policy. Through the proper development of raw materials, the geologist can markedly influence quality control, production and long range planning. Examples of several of the operations of Medusa Portland Cement Co. will illustrate how proper attention to geologic detail pays off in the above areas. Because limestone is the major raw material of port-land cement, the examples will be concerned with it. DEVELOPMENT OF GEOLOGIC DETAIL One of the prime objectives of an exploration or development project should be the establishment of the stratigraphy and structure of the deposit. The basic tool for exploration and development is still the core drill, and the geologist must gain a maximum amount of information from a minimum amount of drilling. In order to obtain this objective the following is essential: 1) Adequate detailed geologic logging of cores. The core is first logged and separated into lithologically distinct units. In order to make the lithologic breaks as meaningful as possible, representative pieces of core (not all) are etched in dilute HCI. This removes the "drill polish", brings out the structure of the rock and indicates the proportion of dolomite and argillaceous material because dolomite and argillaceous material etch in relief. In this way the lithologic breaks become clearer and one gains a general idea of the chemical makeup before analysis. This method of logging lessens the probability of including two types of stone, e.g. limestone and dolomite into the same sample for chemical analysis. 2) Representative sampling for chemical analysis. After logging, the lithologic units are sampled for chemical analysis. A representative analysis can be obtained by extracting a 1-in. sample for every foot of core. For example, a lithologic interval of 10 ft to 20 ft would yield ten 1-in. samples taken at 11 ft, 12 ft, 13 ft... and 20 ft. These samples are then crushed, pulverized and split into a sample for chemical analysis. This sampling method represents a significant saving of time over splitting the entire core. 3) Preparing the core as a record. Because of the expense of storage and the difficulty of handling large amounts of core, only representative samples of each lithologic unit are saved for reference. An

Jan 1, 1965

By J. B. Neale

FRom the beginning of its activities, the members of the National Production Committee have felt that the following points were essential to the success of its work: The operators must feel that their operations were not 100 per cent. efficient; that they should be courteous and fair in their treatment of their employees; and that they should set an example of hard work and patriotic interest in increased production. Every move made must appeal to the sense of fairness of all parties concerned. The men must feel that in working more faithfully, and consequently producing more coal, they are rendering a distinct service to their Government in the time of its great need. As the workers feel that greater efficiency on their part results only in greater profits to the operators, the advantage to the operator should be lost sight of, as far as possible, and the advantage to the Government in fighting the war emphasized. Both operators and workers should know that the Government considered increased production an obligation, and opportunity for service, resting on both parties and not on the operators or the workers alone, and that both parties could very much better the efficiency of the pre-war period. Had the committee intimated that it thought the coal shortage was due entirely to the idleness and inefficiency of the workers, its campaign would have failed, for the men would have resented the charge because only too frequently their efforts to produce more coal were thwarted by bad management; besides, the operators would have lacked stimulus to better effort. On the other hand, had the impression been given that the committee thought that the coal shortage was due entirely to bad management, the operators would have resented the charge because only too frequently their efforts to produce more coal were thwarted by the idleness and inefficiency of the workers; and the workers, having been thus indirectly pronounced 100 per cent. efficient and patriotic, would have lacked stimulus to better effort.

Jan 1, 1920

By Robert Goodwin, Frank R. Milliken

IN September 1939, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1907 to 1919. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about 1 per cent Cu. The chief copper mineral, chalcocite, was disseminated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was probably less than 6o per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a complete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof comprised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig.1, which gives percentages of tonnage and copper content. The tonnage within the limit of the drill holes was estimated at about five million tons with an average content of 0.42 per cent Cu, 31 per cent of which (0.13 per cent) was acid-soluble. A screen analysis of the composite dump sample is shown in Table I. Flotation tests by several companies and individuals were then made, the results of [ ] which ranged from 62 to 74 per cent recovery. On the basis of these, a Zoo-ton pilot plant employing straight flotation was built and operated for a few months. Operation of this plant was unsuccessful, as no provision had been made to handle the copper-bearing solutions resulting from the water-soluble copper, a point that was overlooked in the laboratory test work. Attempts to decant the copper-bearing solution for precipitation in the usual manner ahead of flotation were not satisfactory because of low water recovery (owing to poor settling characteristics of the pulp) and contamination of the copper precipitate with unsettled slime. Low copper prices in 1931 necessitated the termination of testing. With the stimulus of higher copper prices in 1937, a review was made of metallurgical

Jan 1, 1940

By Joseph E. Pogue

THERE are two methods employed in the development of oil pools. The older and dominant method is one in which the primary object is the protection of the underground deposit from drainage through competing wells, and considerations of efficiency of extraction and cost of production are subordinated thereto. The newer and less prevalent method is one in which maximum efficiency and minimum cost are the first objectives and developments to these ends may proceed undisturbed by the exigencies of competitive drainage. The second method has developed mainly in pools under single ownership and the term "unit operation" has come to be applied to this procedure. A single ownership, however, is not essential to the method, for unity of operation may be achieved by agreement under split ownership, or even by a concert of enlightened purpose. There are examples of unit operation where neither the ownership nor the management is a unit, but merely where unity of procedure has been attained, as is the case of the Yates pool. .Throughout this paper unit operation is used in its broad sense without implying sole ownership or single management, although unit operation is more conveniently attained where these conditions are present.

Jan 1, 1930

By George A. Komadina

From its modest beginning in 1957 with one mill grinding section handling 3000 tpd Pima has steadily expanded. In July 1966, work was completed that allowed the concentrator to treat in excess of 18,000 tpd. Almost immediately Pima embarked on another expansion program that will increase plant capacity to 30,000 tpd during the summer of 1967. This repeated expansion has corresponded with the development of additional low-grade ore deposits and with the improved operating economics realized by handling larger masses of material. Early in the life of Pima it was known that a mineralized area was present on the flanks of the high-grade orebody which systematic drilling had shown to be a low-grade copper orebody. Many months of engineering studies revealed that this was sufficient to allow Pima to compete with other large scale, low-grade copper operations in the Southwest.

Jan 11, 1967

Jan 1, 1968

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS ?ARE ASSOCIATES. THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. *AARONS, J. BOYD, Vivian Gold Mining Co., Ltd., Harris, West. Australia. '05 *ABADIE, EMILE R., Cons. and Min. Engr., 214 Union Savings Bank Bldg., Oakland, Cal. '76 ?ABBÉ, MAX F., Prest., Abbé Engineering Co, 220 Broadway, New York, N.Y. '07 *ABBOTT, CHARLES W., Min. Engr. Pioche, Nev. ?08 *ABBOTT, JAMES W., Min. Engr: Ploche, Lincoln Co., Nev. '94

Jan 1, 1917

Jan 1, 1966

By H. J. Struth

In these trying times of proration and low oil prices, it is decidedly necessary for all branches of the petroleum industry to accord full recognition to the economic phenomena that contribute to its varying state of welfare. Perhaps no other single factor has a more important bearing upon the general oil situation than the supply and demand of gasoline. Year after year, the records have shown that the degree of prosperity or depression accompanying the industry's developments has been to a large extent influenced by the degree of balance maintamed between the supply and demand of gasoline. More and more it is being realized within the industry that equilibrium between the supply and demand of gasoline forms the basic structure of crude and product market values and, consequently, the deciding factor in the financial results of the industry as a whole. The influence of the gasoline situation upon the market and financial structure of the petroleum industry was effectively demonstrated during 1930, when excess accumulation of gasoline undermined not only the refined oil market but the crude market as well. In fact, it was a top-heavy gasoline situation that defeated the realization of benefits that might have accrued from an otherwise favorable statistical position in the producing branch of the industry. Indicative of this is the fact that crude oil production was curtailed to the extent of 98,323,000 bbl. last year, while refinery runs to stills were maintained at an excessive rate until late in the year, creating an excess gasoline production of 6,663,000 bbl. above actual requirements. Nevertheless, the movement to curtail refinery operations during the closing months of the year prevented a far worse situation, although it came too late to turn the ebbing momentum of the general oil market. Despite the severe depression of the market values that accompanied 1930 developments, it can be said that the results attained during the closing months of the year, in the direction of production control, marked a decisive turn in the industry's economic affairs. In fact, a review of the oil situation from every angle points definitely to a better general understanding and recognition of the workings of the economic law of supply and demand. As a result, the year closed with crude production in

Jan 1, 1931

By E. Breinan, M. Salkind

Al3Ni whiskers were chemically extracted from unidirectionally solidified Al-A13Ni eutectic ingots, bent into loops, and heated for 0.1 to 10 hr at 320°, 415", and 510°C. The initial strains ranged from 0.003 to 0.055. In all cases, permanent plastic deformation was noted after heat treatment. The deformation consisted of relatively uniform bending at low stresses and temperatures and short times and kinking followed by fracture at high stresses and temperatures and long times. After kinking, the whisker segments adjacent to the kinks were found to have straightened, which is evidence of a dislocation condensation mechanism. The range of temperatures and strains at which time dependent plastic deformation was found indicates that creep of whiskers probably plays a role in the creep of A13Ni whisker-reinforced aluminum. WHISKERS may be defined as nearly perfect single crystals which exhibit high strength. Because they can support high stresses at relatively low strains, they have been successfully employed in reinforcing metals at both ambient and elevated temperatures. In studying the creep behavior of A13Ni whisker-reinforced aluminum at elevated temperatures,1,2 it was noted that the composites exhibited measurable creep deformation. This investigation of the creep relaxation of individual A13Ni whiskel, extracted chemically from the composite was initiated to determine if creep of whiskers could con. "bute to the overall creep of the composite material. Many observations of plastic deformation of metal and halide whiskers have been made. Brenner3-8 noted that copper, silver, and iron whiskers exhibited heterogeneous plastic deformation at room temperature when strained beyond their yield points. Gyulai9 and Gordon10 observed plastic deformation of relatively large (>3 µ) NaCl and KC1 whiskers, although the smallest, most perfect whiskers were completely elastic. Eisner" noted plastic deformation and microcreep of iron and silicon whiskers at room temperature after straining beyond the yield point. Whiskers reported to exhibit creep at stresses below the yield point were zinc1'-" and Silicon.15 Cabrera and price" observed some zinc whiskers which crept at room temperature after a short incubation period but then stopped creeping after a short time. Because some of their specimens exhibited no creep, they concluded that those whiskers that crept were relatively imperfect. Pearson, Reed, and Feldman15 observed similar creep behavior of silicon whiskers at 800°C. They also concluded that creep of the whiskers was a result of imperfections in their crystals. Brenner16 observed delayed failure of A12O3 whiskers at elevated temperatures but found no evidence of plastic deformation up to 2030°C (99 pct of E.EREINAN and M.SALKIND,JuniorMembers AIME,are Research Scientist and Chief, respectively, Advanced Metallurgy Section, United Aircraft Research Laboratories, East Hartford, Conn. Maunscript submitted April 5, 1968. IMD the melting temperature). Brenner also noted7 that some copper and iron whiskers exhibited delayed kinking above 350°C while others did not. One can conclude from these observations that small relatively perfect whiskers could exhibit completely elastic behavior during sustained elevated-temperature loading of composites. Since A13Ni whiskers tested in both bending and tension were found to exhibit no evidence of plastic deformation at room temperature'7'18 this study was initiated to determine whether or not creep of A13Ni whiskers occurred at the elevated temperatures at which creep in the composites was observed. Whiskers were chemically extracted from ingots of unidirectionally solidified A1-A13Ni eutectic, constrained in bending to various elastic strains and heat-treated. The bending constraints were removed after heat treatment and the amount of permanent set was taken as a measure of the time-dependent plastic deformation. EXPERIMENTAL PROCEDURES Ingots of eutectic Al-A13Ni containing nominally 6.2 wt pet Ni were unidirectionally solidified at approximately 11 cm per hr using a process described elsewhere.19,20 The starting materials were 99.99 pct pure. Cylindrical sections cut from the center of each ingot were placed in a 3 pct aqueous solution of hydrochloric acid and the whiskers were extracted as described previously.17 The whiskers nearest the surface were blackened somewhat due to overexposure to the acid while the center of the ingot was being dissolved These partially attacked whiskers were discarded. An intermediate zone of silver-gray-colored whiskers was collected and stored in methanol for use in relaxation experiments. Individual long pieces of A13Ni whiskers were placed on Fisher Precleaned Microscope Slides. These normally straight whiskers were bent elastically into arcs or loops of varying radii by manipulating their ends with a slender probe. The mass attraction between the whisker and the probe was sufficient to cause the whisker to follow the probe. The whiskers were retained in the elastic bend by the surface tension of a fine residual film on the slides. By using long whiskers, the action of the surface tension on the unlooped ends of the whisker allowed high elastic strains to be maintained in the loops. After each whisker was bent, a photomicrograph was taken for use in measuring the bending strain. The range of strains studied was 0.003 to 0.055. The bent whiskers were then encapsulated in Pyrex tubes at pressures between 10"6 and 5 x 10"6 mm of mercury and heat-treated at 320°, 415°, and 510°C (respectively 53, 61, and 70 pct of the peritectic decomposition temperature). After each heat treatment, the liquid film on the slides was found to have dried, but the whiskers were held in their original shapes by a residue on the slide. The minimum radius of curvature of each bent whisker was measured before and

Jan 1, 1969

By F. Robertson Jones

IF the tendency toward extending the scope of the workmen's compensation system to include life, health, accident, old age, and unemployment insurance for workers is not promptly altered, I believe there will be a complete breakdown of that system. This is not because of any objections, there may he to requiring industries to provide these additional forms of protection in whole or in part to their employees. It is rather because our workmen's compensation laws, their scale of benefits, and the administrative procedure under them are not adapted or suited to such situations. If the compensation principle is limited to its own proper sphere and is not enlarged so as to include all the ills that the flesh is heir to, it is practical, "workable, and beneficent. If it invades foreign realms, it is bound to grow into a veritable Frankenstein' which will harm principally those it 'is supposed to aid, and, at the same time, will promote waste, fraud, and Industrial demoralization. Compensation risks will become almost uninsurable; the cost to business will be intolerable; and the development of sound relief measures which will give to labor the protection now sought by the uneconomic device of enlarging the compensation law territory will be retarded.

Jan 1, 1934

By Irwin Roman

IN a previous paper,1 a method was suggested for determining the depth to a bed in the simple case of a uniform overlying layer of constant thickness. The main purpose of the present paper is to show how a slight modification of that method has been used to interpret specific data obtained in the upper peninsula of Michigan by the staff of the Depart- FIG. 1.-THE TECTONIC CONFIGURATION. ment of Mathematics and Physics of the Michigan College of Mining and Technology. The method of Tagg2 has also been used on the same data, thus furnishing a comparison of the e two methods, as well as a method of using the two methods jointly. The method of measuring the apparent resistivity is that suggested by Wenner,3 and illustrated in Fig. 1. A current I enters the earth at the positive pole C and leaves it at the negative pole D. The potential V of the high electrode A, with respect to the low electrode B is measured by suitable means. The separation of the collinear points in the order shown, DBAC, is 1, the same. for each interval.

Jan 1, 1934

By William Priestley

The author has shown, by .practical experiments, how the rate of cooling steel in the mold governs ingotism, segregation, the formation of dendrites, and the distribution of intergranular material; and the resulting effect these conditions have on the physical qualities of the steel before annealing, after annealing, and after forging. The paper also describes how the structure of steel is affected by the design of the mold and the method of pouring. It is shown that the various constituents of carbon steel segregate differently under different rates of cooling. For the classes of steel covered in this paper, it is concluded that the best physical structure and the most uniform chemical composition is obtained by pouring the steel at a low temperature and solidifying as rapidly as possible in the mold. MUCH time has been devoted, by metallurgists, to the study of steel after solidification and remarkable strides have been made in the heat treatment of steel, but less knowledge is available of the thermophysical, activity of the constituents of steel prior to solidification in the mold. It is known that certain elements added to steel produce marked changes in physical properties, also that other elements added to steel produce similar changes, but we have only meager knowledge as to how these elements combine in steel under different conditions of solidification. It is not sufficient to know, from chemical analysis, that a certain element is present in steel. We should know how this element is in combination with the other elements and whether the combination is such as will give the greatest physical properties. Certain elements go into solid solution with the iron, while others segregate to the grain boundaries and combine with the impurities collected there. Until it is known where an alloy produces the most beneficial effect and a means, is determined for controlling its physical location by altering solidification conditions, or otherwise, we will not obtain the maximum value from our alloys.

Jan 2, 1924

By G. C. RIDDELL

THE metallurgist, chemist, and physicist are blazing trails that lead far afield. Pushing on into an "Alloy Age" they see a non-ferrous era over- taking iron and steel. Delving into the nature of the physical world, they break down a supposedly indivisible element, hydrogen. Not content with terrestrial problems, they peer back along the cosmic ray into iaterstellar space, glimpsing forces that are, apparently, still busy with the task of atom-making. Mastering and organizing the material and physical, they advance steadily toward that borderland of science where the concept of matter itself seems abandoned, and force is the substance left.

Jan 1, 1930

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.'-' 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 A. Totani, S. Nakajima, H. Okazaki

The phase diagram for the SnTe-SnSe system has been studied in the temperature range from 300° to 900°C by differential thermal and quenching techniques. The X-ray measurements were made on quenched specimens. High-temperature diffraction was also made to study the phase transition in SnSe. The system is proved to be of a eutectic type in which no intermetallic compound exists. The eutectic point is at the composition SnTeo.55 Seo.45. the eutectic temperature being 755°C. Solid solubility limits are SnTeo.6Seo.r and SnT eo. 3s Seo.6s at the eutectic temperature, and change almost linearly to SnTeo.aaSeo.lz and SnTeo.18 Seo.az as temperature decreases to 300°C. It was shown that the SnSe phase has a phase transition of the second order at about 540°C and that the transition temperature decreases with increase of the SnTe content. THERMOELECTRIC properties of tin telluride (SnTe) and tin selenide (SnSe) have been studied extensively in recent years. The variation of physical properties with composition could be of interest if these compounds form an appreciable crystalline solution. The purpose of present investigation is to confirm the formation of crystalline solution or intermetallic compound, if any, and to establish the phase diagram for this system. The crystal structure of SnTe is NaCl type with a cubic unit cell1 (a = 6.313A). The crystal of SnSe having an orthorh2mbic unit cellz (a = 11.496, b = 4.1510, and c = 4.4437A) is isomorphous with tin sulfide (SnS) which has a distorted sodium chloride structure. It has been known that SnSe has a phase at at 540°C; the transition has been assumed to be of the second order. As far as we know, only two studies on the SnTe-SnSe pseudobinary system have been reported. The conclusion obtained in these papers is that, in the composition regions near SnTe and SnSe, the system forms a crystalline solution of the SnTe structure and the SnSe structure, respectively, and that, in the intermediate region, both phases coexist. However, neither the variation of the solid solubility vs the temperature nor the liquidus and solidus were investigated. Hence present writers have attempted to determine the phase diagram of the system by differential thermal analysis (D.T.A.) and X-ray diffraction. EXPERIMENTAL Sample Preparation. Starting materials, SnTe and SnSe, were prepared by the direct fusion of commercially available high-purity (99.999 pct) elements. Stoichiometric amounts of each couple Sn-Te or Sn-Se were weighed into a clear fused silica ampule. After evacuation to a pressure below 10-3 mm Hg, the am- pule was sealed, and annealed at 900°C for 5 hr. The melt was quenched in water. X-ray analysis confirmed the formation of a single phase of SnTe or SnSe. The other samples, SnTel-,Sex were synthesized from these SnTe and SnSe by mixing them in the required ratio, followed by annealing at 900°C and quenching. These samples were used directly for D.T.A. For X-ray measurements, samples were annealed at 700°, 600°, or 500°C for 100 hr or at 300°C for 150 hr, and then quenched in water. It was found that the lattice constants of the SnTe phase annealed for 150 hr at temperatures above 500°C did not differ from those annealed for 100 hr at the same temperatures. However the X-ray phase analysis showed that at 300°C the annealing for 150 hr was necessary to attain a true equilibrium state. D.T.A. The solid-liquid equilibrium temperature was determined from D.T.A. measurements. The sample was sealed in an evacuated silica tube and molybdenum powders sealed in an another tube were used as a reference material. The sample and the reference tube were placed in a nickel block and were heated from room temperature to 900°C at a rate of 3°C per min and then cooled down at the same rate to 600°C. Thermocouples for these measurements were Pt-Pt. Rh (10 pct) and the error of temperature measurements was within + l0C. D.T.A. curves were obtained on a two-pen recorder and an automatic controller (PID type) was used for the program of heating and cooling. When temperature reaches the solidus from the low-temperature side, there appears an endothermic peak. The solidus temperature was determined by extrapolation of the straight portion of the starting flank of this peak to the base line. In a similar way, the liquidus temperature was determined from an exothermic peak on D.T.A. cooling curve. In the case of supercooling, if any, its degree can be estimated from the magnitude of the abrupt temperature rise. X-Ray . X-ray powder patterns were taken by a diffractometer using CuK, radiation. Since the SnSe crystal is cleaved easily, the powders become flaky when SnSe-rich samples are ground in an agate

Jan 1, 1969