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By D. Argyriades, G. Derge, G. M. Pound

The electrical conductance of molten FeS was studied as a function of temperature and composition. It was found that stoi-chiometric FeS (36.5 pct S) shows a minimum specific conductance of 400 ohm-1 cm-1. For the Fe-rich melts the conductivity increases with increasing amount of iron to about 4850 ohm-1' cm-I at 26 pct sulfur. For the sulfur-rich melts the conductivity increases with increasing amount of sulfur until it reaches a maximum of 1300 ohm1 cm-1 for 37.4 pct S and decreases to 800 ohm-1 cm-1 for 38.3 pct sulfur. It is concluded that molten stoichiometric FeS is an intrinsic semiconductor in which the forbidden gap in the electron energy level diagram is quite narrow. Excess sulfur acts as an acceptor impurity in providing a component of positive hole conduction, while excess iron acts as a donor impurity to increase the n-type conduction. K. Bornemann and G. von Ftauschenplatl used a four-terminal, direct-current cell to study the electrical conductance of molten copper sulfide. Their measurements showed a high conductivity, of the order of 100 ohm-1 cm-" and a positive temperature coefficient. From electrolysis studies, Savelsberg2 concluded that molten Cu2S and molten FeS are electronic conductors. Further. he found that molten FeS has a high specific conductance, of the order of 1500 ohm-' cm-', and a small negative temperature coefficient. Pound, Derge, and Osuch,3 using an ac Kelvin circuit and a four-terminal cell, measured the specific conductance of molten Cu,S, molten FeS, and various mixtures. They found that the specific conductance of the solutions followed a roughly additive rule of mixtures. Yang, Pound, and Derge4 showed from electrolysis measurements that the mechanism of electrical conduction in molten Cu2S, FeS, and mattes is primarily electronic. Further, they observed that small additions of CuCl suppress the electronic conduction whereupon the system behaves ionically.

Jan 1, 1960

By Charles White Merrill

Money is one of the most pervasive elements in human life. The compensation for a workman's daily efforts is expressed as a wage and is measured in money. What an individual may consume depends largely on his income which also is expressed in terms of money. If he would start an enterprise its size would be determined in large part by the amount of money available for capitalization and its success would be measured in net income expressed in money. In short, the most widely used common de- nominator for comparing merchandise, real property, jobs, enterprises, gross national product, or personal success is money. Despite this use of money by almost everyone past infancy to express his appraisal of the innumerable values he sees around himself, the complexity of the device called money makes its nature and workings a mystery to most users. Some of the difficulty in understanding money results from the fact that it has three distinct but interrelated functions: (1) a medium of exchange, (2) a unit of account, and (3) a store of value. In many statements about money the discussion moves from one function of money to another without the speaker or the listener recognizing the changes. For example, the housewife says "We took the money we had saved up to make the down payment and after twelve monthly payments the television will be ours." When this housewife spoke of "saving up the down payment" she referred to money in its function as a store of value; when she spoke of "the down payment" she was using money as a medium of exchange; and when she referred to the "monthly payments" she spoke of money as a unit of account. Another cause of confusion in understanding money is its paradoxical nature in that it represents both the power to produce and the power to consume. For example, when the rich uncle dies one nephew may regard his inheritance as an opportunity to buy a farm and leave the ranks of the wage earners to become an independent producer, whereas the other nephew may regard his portion as the means of living in complete leisure as a pure consumer.

Jan 1, 1964

By W. Mostowitsch

Lead sulphate occurs as anglesite, and is formed in every roasting of lead sulphides or sulpho-salts containing lead. In smelting in the blast furnace an ore containing natural or artificial lead sulphate, a large part of the sulphur present goes to the formation of the intermediary product matte which requires further treatment for the recovery of the values it contains. It is therefore of importance to study the behavior of lead sulphate at elevated temperatures, both without and with reducing agents, especially as the information available gives data which are more or less conflicting. 11. Decomposition of PbS04 by Heat The dissociation of PbSO4 into PbO and SO3 or SO2 and 0 has been discussed by many metallurgists. The following data are considered to be representative. Doeltz and Graumannl found that PbS04 was not affected-by heat at 800" C.; that dissociation began at 900" C., and was rapid at 1,000° when the salt lost in 1 1/2 hr. 14.3 per cent. of its weight, the dry salt containing 26.43 per cent. SO3. Hofman and Wanjukow2 summarize their work upon the dissociation of metallic sulphates with the statement that the decomposition of PbS04 begins at 195' C., but progresses very slowly, with the formation of the basic salt 6PbO.5SO3 at 705"; that this salt undergoes a transformation at 847") begins to be decomposed at 888") to sinter at 896", and to fuse at 910"; rapid dissociation begins at 952") and is accompanied by volatilization of PbO; retardations at 958" and 962" indicate an acceleration of decomposition which, however, is not complete. Proske3 found that PbSO4 gave off at 900" C. in 30 min. only 0.63 per cent. of its 803, and that the loss increased with

Jan 1, 1917

By W. Mostowitsh

I. Introductory LEAD sulphate occurs as anglesite, and is formed in every roasting of lead sulphides or sulpho-salts containing lead. In smelting in the blast furnace an ore containing natural or artificial lead sulphate, a large part of the sulphur present goes to the formation of the intermediary product matte which requires further treatment for the recovery of the values it contains. It is therefore of importance to study the behavior of lead sulphate at elevated temperatures, both without and with reducing agents, especially as the information available gives data which are more or less conflicting. II. Decomposition of Lead Sulphate by Heat The dissociation of PbSO4 into PbO and S03 or S02 and 0 has been discussed by many metallurgists. The following data are considered to be representative. Doeltz and Graumann1 found that PbSO4 was not affected by heat at 800° C.; that dissociation began at 900° C., and was rapid at 1,000° when the salt lost in 1 ½ hr. 14.3 per cent. of its weight, the dry salt containing 26.43 per cent. SO3. Hofman and Wanjukow2 summarize their work upon the dissociation of metallic sulphates with the statement that the decomposition of PbSO4 begins at 195° C., but progresses very slowly, with the formation of the basic salt 6PbO.5S03 at 705°; that this salt undergoes a transformation at 847°, begins to be decomposed at 888°, to sinter at 896°, and to fuse at 910°; rapid dissociation begins at 952°, and is accompanied by volatilization of PbO; retardations at 958° and 962° indicate an acceleration of decomposition which, however, is not complete. Proske3 found that PbSO4 gave off at 900° C. in 30 min. only 0.63 per cent. of its SO3, and that the loss increased with

Jan 5, 1916

By M. W. Von Bernewitz

AN important regional meeting of the American Institute of Mining and Metallurgical Engineers was held, at Salt Lake City on Aug. 22 to 26, jointly with the fifth annual meeting of the Western Division of the American Mining Congress. The whole meeting was marked by enthusiasm, keen attention to the subjects under discussion, and many renewals of personal contacts. The trips to the various plants were well attended and the local press paid much attention to the meeting. The A. I. M. E. sessions began Aug. 23, with a non-technical morning session. J. 0. Elton, manager for the International Smelting Co., presided. The purpose of this session was to present in a non-technical manner the relation of flotation to mining, smelting, and the State. Ernest Gayford, metallurgist with the General En-gineering Co. of Salt Lake City, gave the definitions of flotation as suggested by Rickard, the dictionary, Weinig, and Taggart. The active agent in flotation is the air bubble, and the two prime requisites are the formation of bubbles and the creation of selective action of the bubbles for metallic particles instead of for gangue particles. Broadly, all the sulfides are floatable minerals, but the oxides, carbonates, silicates and sulfates are not. As far as Utah is concerned, flotation has been one of the greatest means of conserving its natural re-sources, because it has converted millions of tons of waste rock into pay ore; it is recovering millions of pounds of metal formerly lost in tailings; it has con-verted the zinc from a liability into an asset; and has kept thousands of men at work and distributed millions in dividends for the benefit of the State. As to the future of flotation, Mr. Gayford can con-ceive that the next 5 or 10 years may see as much, if not more, advance than was made in the preceding period. The big problem is dressing oxides, carbonates, silicates, and sulfates, and simplification of the number of reagents, also the separation of different gangue min-erals from one another.

Jan 10, 1927

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By Sherwin F. Kelly

THOUGH the Geophysics Commit- tee limited itself to two sessions this year, both of them marked by a high percentage of absentee authors, even this situation failed to dampen the and or of the ebullient geophysicists, who bandied no small amount of good- humoredlv barbed discussion. Hans Lundherg offered some constructive criticism of last year's report by the Geophysics Education Commit- tee, making a plea for more training in field techniques and less insistence on rigorous theoretical training. Carl Heiland pointed out the necessity of making geophysics and geology courses more attractive in order to draw more students into these fields. Exception was taken to this line of reasoning by Father Macelwane and Sherwin F. Kelly who emphasized the necessity for sound basic training if competent geophysicists were to be turned out. This discussion developed apropos of the report of the Geophysics Education Committee, which had been postponed from the Education Division meetings, but was not read as it was available in mimeographed form. Except for this diversion the morning program fol-

Jan 1, 1944

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By Victor J. Miller

The Northeast Tripp Slide is one of the larger slope failures that can be attributed to open pit mining. It is a 11.7 million cubic meter (15.3 x l0 6 yd3) wedge failure created by two thick gouge-filled fault zones whose intersection plunges into the Tripp pit at 13°. One unique aspect of this failure is that the slide is now stable despite having moved an estimated 8.5m (28 ft.) towards the pit and having reached a maximum overall velocity of 2lmmlday (0.07 ft/day). The slide started to fail in 1968, accelerated until mining in the slide's toe area was halted in April 1970, then began to decelerate. With the cessation of mining in the toe area, rubblized rock sloughed into the pit bottom which added weight to the failures toe constraints and began the stabilization process. Measurements from a network of survey stations revealed a correlation between the slide's velocity and heavy precipitation. Runoff water accumulating in the tension cracks is believed responsible for this correlation. Moreover, the survey net measurements showed that during the failure's last stage the vertical component of the slide's movement greatly increased. It is proposed that this settling was caused by plastic-like flowage of the clay gouge underlying the failure The fault zone's effective shear strength was estimated by a back- analysis on the wedge's geometry and by performing direct shear tests. The tests, performed on cores taken from samples that were collected on the failure, yielded a residual shear strength of: cohesion 0.61 kg/cm2 (8.7 lb/in2), and a friction angle of 9.6°. This residual shear strength was near1y equal to the back-calculated strength indicating that the controlling fault's effective strength was essentially the same as the residual shear strength of the gouge filling

Jan 1, 1983

By J. F. Lewis

Much has been written on this great engineering work, principally from the civil engineer's stand-point. In presenting the subject to the Institute, it seems necessary to include something of geology as well as engineering. In this case, it is particularly the glacial and post-glacial periods with which we are concerned; for it has been clearly proved that the canal recently excavated has not for the first time opened the Des Plaines valley for drainage away from Lake Michigan, and that this valley, as well as the site of this city, is very closely connected with the processes and effects of the ice period. We have simply renewed a channel and a drainage direction which formerly existed. As the days of deep water-ways for commercial purposes are fast approaching, engineers may find the consideration of ancient topography and geologic changes highly useful. For what I may say on this subject I am greatly indebted to Mr. Ossian Guthrie, who has made an earnest study of glacial geology and labored especially to decipher the records of its history in this region. * Chicago is situated in the track of one of four great glacial ice-streams that swept down from the North: one moving due South from Marquette and entering the Illinois valley at Ottawa; one through the Lake Michigan valley, entering the Illinois valley near Lemont; one from Saginaw Bay diagonally across the States of Michigan and Iadiana, entering through

Jan 1, 1898

By E. P. Pfleider

Important economic planning by industries, companies, financial firms and governments is predicated on estimates of future growth potential. Prior to the passage of the Taconite Amendment by the people of the State in November 1964, various admittedly conservative forecasts were made of the future of Minnesota's iron ore industry. Since that date, 3 new taconite plants are under construction, 2 are being expanded, one has just gone "on stream," and a seventh is in the design stage. These plants have a total capacity of about 35 million tons of pellets annually. The pessimism of 1964 today is being replaced by unbounded optimism. In the light of such recent developments, it becomes essential to update forecasts related to production, employment and capital investments. New projections show 50 to 58 million tons of pellet production from Minnesota by 1975. This tonnage, together with some 6 to 8 million of natural ores, should provide an annual full-time employment of 15,000 by the mining companies, plus 700 in related railroad and power producing activities and 1000 in plant construction. Total capital investment in new plants should reach $1.5 billion by 1975 and $2 billion by 1990. These current estimates indicate that the conservative goals as set in 1964 for the year 1990 should actually be achieved by 1975 or 1980. BACKGROUND Various forecasts1,2,3 have been made of the future consumption and production of iron ores within the United States. The most recent of these is by Harrison,1 delivered at the American Mining Congress meeting in Las Vegas in October. His estimates reflect the latest iron ore developments on a world wide front as well as the accelerating trend toward pellets. Minnesota's Natural Resources council prepared a detailed report in 1964 outlining the various factors that affect the future of Minnesota's iron ore industry. It presented estimates predicated on the

Jan 1, 1967

By R. A. Falconer, H. L. Lovell

With increasing requirements for fine coal cleaning and the many advantages of the cyclone operating on a coal-water slurry, a series of studies designed to achieve an enhanced understanding of the cyclone parameters has been pursued. The purpose of this investigation has been to vary a series of dimensional parameters with an experimental 15-in. diam hydro-cyclone, and to determine the relative effects of parameter variations upon ash and sulfur removal. This study of the hydrocyclone is a continuation of a series of investigations, conducted in the Dept. of Mineral preparation at The Pennsylvania State University, which are directed toward the removal of ash and sulfur constituents from fine bituminous coal by size-density separations in cyclones, and toward a fuller understanding of the complex mechanisms involved in such separations. The purpose of this investigation has been to vary a series of dimensional parameters with an experimental 15-in. diam hydrocyclone, and to determine the relative effects of parameter variations upon ash and sulfur removal. Of special interest was the response to cone angle variation, since it is the high included cone angle that generally distinguishes the hydrocyclone as a gravity separator rather than a classifier. DESCRIPTION OF THE HYDROCYCLONE Fig. 1 is a dimensional drawing of the hydrocyclone used in the investigation. The unit was designed and fabricated by Heyl and Patterson, Inc., for experimental use. The dimensional parameters considered were: 1) Three cone sections having included angles of 45, 60, and 95,degrees, 2) Three 3 1/8 in. diam vortex finders having lengths of 15, 17, and 19 1/2 in., 3) Three 4 1/16 in. diam vortex finders having lengths of 15, 17, and 19 1/2 in. 4) Two apex sections having diameters of 2 and 2 1/4 in. The feed inlet orifice had a fixed diameter of 3 in. The hydrocyclone test installation was made at The Pennsylvania State University pilot plant at Barnes-boro, Pa., which operated at 50 tph. During the period that the hydrocyclone was tested, research was in progress at the Barnesboro site to reprocess refuse material from a near-by coal preparation plant in

Jan 1, 1968

By John V. Beall

STREAM pollution caused by waste waters from mineral industry operations is a problem that has grown up with the industry. Its importance to each operator is dependent on the amount and type of waste he dumps into the rivers and streams; on whether this waste pollutes the waters sufficiently to make them unfit for potable water, irrigation, and conservation of wild life; and on whether this waste makes a safety or health hazard. Through the years our growing population and industry have made increasing demands on the mineral industries, the suppliers of the raw materials on which our industries are based; and we have met these demands at some sacrifice to the natural beauty and cleanliness of our country. However, that is often the unavoidable nature of the business, and along with the increased use of our

Jan 1, 1948

MARCH 15-Industry is rapidly snapping back from another coal crisis, other business news is in general favorable and the outlook through the Spring is by most observers considered quite promising. Most industries report comfortable backlogs of unfilled orders, department store sales in recent weeks have equalled in dollars those of the corresponding period last year, retail sales of automobiles show again over the same period a year ago, and new orders for machine tools are at the highest figures since August 1946. Orders for railway freight cars have shown a very encouraging pickup, with a total of 9385 cars in January and the N. Y. Central alone ordering 4500 in February. Construction continues very active. In January new housing starts totaled 80,000 against 50,000 a year ago and the daily average contract awards, according to the Dodge reports, were 57 pct larger. In the first 22 days of February the increase in awards was 27 pct. Lumber orders since Jan. 1 have run 22 pct above last year. All of these favorable factors bolster the opinion that the upturn in industrial output and employment which began last summer has not yet spent itself and that the setback caused by the strikes will be made up when people get back to work. Only in a few lines are there indications that primary production may be outrunning the consumption of finished goods, although inventory build-up would seem to be rather modest as the National Association of Purchasing Agents reported in February that 78 pct of its members were buying for 60 days or less. Industrial prices as a whole show no significant trend despite the continued alarm over both the immediate and the long-term possibility of inflation caused primarily by the government's increasing expenditure and its inability to balance the budget. A recent advance of 1.9 pct in primary market prices is viewed by some people as the surface symptom of renewed inflation, but even so it is more than two years since the alltime high was reached by the daily index of sensitive commodities in November 1947. Over two years have passed since prices received by farmers hit their peak and about a year and a half since all wholesale prices and the consumer price index touched their highest points in August 1948. The decline in the wholesale price index has been almost continuous, interrupted only twice by slight advances in the monthly figures from February to March 1949, and, later in the year, from August to September. Of course, this continued decline in the last half of 1949 largely reflects a downward movement in farm and food prices. Wholesale prices for commodities other than farm and food leveled out after June and now stand only slightly under the June level. Farm products are down by 22 pct from January and by 18.6 pct from August 1948. Food prices are down only slightly less. Consequently, the farm price support program is in serious trouble and has imposed a heavy financial burden on the Treasury. In those commodities other than farm products only building materials, chemicals and textiles have come down as much as the average, while housefurnishings and metals and their products have fallen hardly at all. Glancing away from the domestic front, the results of the British general election indicated a highly inconvenient situation, that public opinion there is so exactly deadlocked as to divest the victors of much ability to make forceful decisions or create significant policy. It is generally considered that another election in the near future would give substantially the same result. The British people are equally divided and the politicians are not likely to precipitate another appeal to the country until there is manifest reason to believe that external and internal circumstances have changed sufficiently to permit one party or the other to obtain a decisive verdict. Because of the lack of a clear mandate steel nationalization will likely lag in Britain. In the meantime there is considerable discussion going on as to whether the European steel industries as a whole are at a disadvantage in world competition with the American industry. An article in the "Statistical Bulletin" for January of the British Iron and Steel Federation takes issue on this point with the authors of the Geneva report, observing that they wrote before devaluation, and this particular conclusion "has been overtaken by events." The "Bulletin" also contends that the statement was in any case incorrect so far as Britain was concerned, and that it was based on scanty and insufficient evidence. To support the rebuttal a detailed and extensive comparison is made of the home prices of certain steel products in Britain and in other countries of the world. The accompanying table gives a selection of the prices published. It sets out the changed position since devaluation and since the recent increases in American steel prices. These are home market prices; no doubt in competitive export business some of the price levels could be brought closer together at need.

Jan 4, 1950

By John J. Gilman

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

Jan 1, 1957

By 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. G. Allten

EXAMINATION by metallographic and X-ray diffraction means of an austenitic steel containing 0.06 pct C, 1.26 pct Mn, 0.38 pct Si, 21.15 pct Ni, 18.72 pct Cr, 3.07 pet W, and 9.14 pet Mo indicated that a - phase, which had not been reported in the literature, existed in this steel. Both the s and car-bides of the M6 C type were present in the as-forged steel. The carbides dissolved completely in the aus-tenite at approximately 2200°F (1205°C). The s, however, was present at all temperatures up to the solidus temperature of the steel at approximately 2375°F (1300°C). Ferrite was not found in any condition of the steel. The faintness of some of the s lines in X-ray patterns obtained from samples of the steel made it desirable to isolate the s prior to verification of its entire pattern. It was found that the s phase could be separated from samples of the steel which had been water quenched from 2250°F (1230°C) by dis-

Jan 1, 1955

THE shipments of high-grade manganese ore, con-taining 35 per cent or more of manganese, from the mines in the United States in 1926 were slightly less than half as large as similar shipments in 1925, accord-ing to the United States Bureau of Mines, Department of Commerce. The shipments in 1926 by 45 producers amounted to 46,258 long tons as compared with 98,324 long tons by 42 producers in 1925. This decrease was due to the falling off of the shipments from Montana. The domestic production of metallurgical ore in 1926 was 26,530 tons; that of chemical ore, 19,728 tons. Montana was the largest shipper with 5713 tons of metallurgical ore and 17,904 tons of chemical ore. The largest individual shipper of metallurgical ore was the Crescent Mine in the Olympic Mountain Region, Clallam Co., Washington, from which the shipments for the year were 3162 tons. The mine was operated by lessees and reverted to the owners in July, and thereafter to the close of the year no .ore was shipped.

Jan 6, 1927

US Tin Mission To Study Costs in Far East A move to obtain adequate supplies of tin at prices the United States is willing to pay was initiated when the interagency tin mission left for the Far East. The Mission, which includes representatives of the Reconstruction Finance Corporation, State Department, Defense Minerals Procurement Agency and the Bureau of Mines will go to Indonesia and Malaya. The primary purpose of the mission, according to officials, will be to study tin production costs, not to negotiate for the purchase of tin. The mission will be prepared to enter into negotiations, if the Far Eastern producers are amenable. The United States withdrew as a large-scale buyer of tin some months ago in protest against what it considered exorbitant prices being charged in the Singapore market. Subsequent attempts to negotiate for a steady tin supply at what this country considers reasonable prices have been unavailing. The U. S. is prepared to enter into a two or three year contract with the price of tin somewhere between $1.00 to $1.12 per lb. The decision to abstain from the market has not yet put a squeeze on U. S. supplies. Substantial quantities of tin still are coming in from Malaya under an old contract.

Jan 12, 1951

By OTTO HERRES

TITANIUM is estimated to be the ninth most plentiful element, ranking after iron, aluminum, and magnesium, and ahead of copper, lead, and zinc. Vast quantities of titanium are widespread throughout the world in ore deposits and beach sands. Before the war, processing plants were operated in England, France, Italy, Czechoslovakia, Norway, Russia, Australia, United States, and Japan. In spite of its widespread occurrence, however, the U. S. Department of Justice has held the titanium industry to be a world monopoly and action was taken in the Federal court during the summer of 1945 to enjoin international patent and marketing agreements and to restore free competition. Possibly the rather surprising lack of public familiarity with this industry of international importance arises from its astonishingly rapid development and growth in the strong hands of some of the greatest chemical companies in the world, including the important foreign companies, Imperial Chemical Industries (British), Montecatini (Italian), I. G. Farben (German), and Titan Kogko Kabushiki Kaisha (Japanese). The rapid growth of the titanium industry in the United States is indicated by a tenfold increase of ore imports in the 1930 to 1940 decade before the war began to affect shipments from overseas. The fact that the industry formerly derived practically all ore for chemical processing in American plants from foreign sources probably also accounts for lack of general public knowledge of titanium. In 1939, to meet the requirements of increasing demand for the white pigment. titanium dioxide, more than 250,000 tons of titanium concentrates moved to this country, principally from the Travancore coast of India where the ilmenite concentrate from the beach sand runs as high as 60 per cent in titanium dioxide. Global warfare put a stop to shipping and thus gave rise to the development of titanium mining on a substantial scale in the United States during 1941.

Jan 1, 1946