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By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,' published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By O. S. True, C. H. Herty

It is well known that manganese will desulfurize molten iron through the formation of manganese sulfide, which, being only slightly soluble in the metal, rises to and enters the slag where it remains as such (mixer slag) or is converted partly or wholly to calcium sulfide (basic open-hearth slag). The reaction by which manganese sulfide is formed is Mn + FeS = MnS + Fe. This reaction is generally considered to be reversible, although McCancel states that such is not the case. The experimental work was carried out to confirm the results of Roh12 as to the reversibility of the reaction. Six trials are herein considered. In each 200 gm. of electrolytic iron free from manganese and sulfur were melted in a pure zirconia crucible in a carbon resistance electric furnace. To the melted iron in runs 2, 3 and 4 metallic manganese and manganese sulfide were added to give 1, 2 and 4 per cent. manganese respectively, with 0.50 per cent, of sulfur in each. In runs 5, 6 and 7, metallic manganese and iron sulfide to give the same proportions of. manganese and sulphur as in runs 2, 3 and 4, were added. The melts were held molten in the furnace for an hour and then cast into small ingots. The results of these melts are as follows: Ingredients of Charge Analysis or InRot ManOaneBe, SulfUR, ManOaneBe. SULFUR, Run Material Charged PeR Cent. PeR Cent. Per Cent. PeR Cent. 2 MnS + Mn............... 1.0 0.452 0.636 0.367 3 MnS + Mn............... 2.0 0.50 1.57 0.310 4 MnS + Mn............... 4.0 0.50 2.81 0.230 5 FeS + Mn................ 1.0 0.50 0.647 0.397 6 FeS + Mn................ 2.0 0.50 1.45 0.374 7 FeS + Mn................ 4.0 0.50 2.73 0.195

Jan 1, 1925

By Alfonso W. Ovalle

INTRODUCTION The block-caving mining method is one of the most economical ways existing today to extract ore from nature. It is undoubtedly the least costly of the underground systems and moreover it compares favorably to open-pit mining. In addition to its low cost characteristic, the block-caving mining method permits a great extraction volume as can be exemplified by El Teniente's output capacity of over 22 million tons of ore per year. These characteristics of block-caving give assurance that, even though it is a very old mining system, it will be a good answer to the many future large massive low ore grade deposits to come and a1 so to rep1 ace open-pi t mining as such operations get deeper with higher stripping ratios. These are the reasons that induce further study of block-caving. In this paper block-caving at El Teniente is analyzed with due consideration to the major problems that this mine will encounter. Emphasis is given to the factors influencing the mining of soft ore which accounts for most of the ore to be extracted in the next ten years. A separate paper is devoted to a major modification introduced to block-caving hard primary ore at El Teniente by means of LHD equipment extraction. DESCRIPTION OF THE PRESENT MINING Ore Production and Flow Over 62.000 tons per day of ore are extracted 359 days per year at the El Teniente Mine. The Teniente 8 train haulage level at 1.983 m takes 29.000 tons daily to the Col6n Concentrator. Two trains make the 8 km haul with 16 cars per train. Car capacity is 90 tons. The Teniente 5 train haulage level 298 m above takes 33.000 t per day to the old Sewell Concentrator. Ore is produced from three production areas in two different levels. The so called North Mine produces 42.000 tons daily from the Teniente 4 level 65 m above the Teniente 5 haulage level. The Central Mine produces 1.000 tons from the first hard rock block caved at the Te- niente 4 level. The combined 43.000 tons per day production is sent through inclined 2 m dia- meter raises to the Teniente 5 haul age level , where 33.000 tons are taken 2.5 km to the Sewell Concentrator and 9.000 tons are hauled 0.5 km to a 5 m diameter vertical ore pass which sends ore to Teniente 8. The haulage is by 7 trains, 15 gabble-bottom cars per train. Car capacity is 20 tons. The so called South Mine produces 19.000 tons per day from the Teniente 1 level 645 m above the Teniente 8 haulage level. Ore is transferred by 2 m diameter inclined raises to the Ten 1 Retram level 22 m below, where 5 trains with 20 Sandfor Day cars per train, 8 tons capacity per car, haul the ore 1.5 km to two vertical 5 m diameter ore passes which connect to Ten 8. Starting in 1982 the Central Mine will in- crease production to 6.000 tons per day. An in- dependent loop haulage system will start operat- ing at the Teniente 5 level to feed a new under- ground 1.372 mm (54 in.) gyratory crusher which will send minus 152 mm ore (9 in.) to Teniente 8. In two or three years time the North Mine will only feed the 33.000 tons to the Sewel 1 Concentrator with its old Teniente 5 haulage system. The Col6n Concentrator will be fed from the Central and South Mines. Figure 1 shows the transfer systems and ore flows. The Ore Body In plan view at the Teniente 4 level the ore body has a kidney shape 1.800 m long and between 400 to 700 m wide. The north-eastern section of the ore body was washed away by the Teniente River. At the Sub 5 Level, 125 m below Teniente 4, the mineralization completely surrounds the circular 1.000 m diameter steep-sided barren breccia pipe (Braden pipe) . The ore body rock is 73% andesite, 14% diori te, 13% dacite and 6% mineralized breccia. Most of this ore is secondary enrichment sulfides which apart from the dacite is strongly fractured being chal cocite, cove1ine , bornite and

Jan 1, 1981

Reynolds Jamaica Mines, Ltd., has received a $3+ million loan from ECA for the development of what are termed the largest bauxite deposits in the world in Jamaica, B.W.I. This amount is in addition to $11 million already provided. The new agreement calls for delivery of 750,000 tons a year beginning in early 1952. Inco has announced a new alloy containing 35 pet Ni which can be used for many purposes served by the old alloys which ran up to 70 pet Ni. The new alloy "Incoloy" is 35 pet Ni, 20 pet Cr, and the balance iron.

Jan 8, 1951

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.'-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4'5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,'-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By W. A. Barrows, Carl Zapffe

Jan 1, 1913

By C. K. Leith, W. J. Mead

One of the most significant developments in the iron industry in recent years has been the discovery and opening of enormous reserves of low-grade ore in eastern and northeastern Cuba. The two principal fields are the Mayari and the Moa, situated on Nipe bag, in the Province of Oriente. A less well-known district of the same type is that of Baracoa, at the east of the island, and another is in Csmaguey Province in central Cuba. In the comprehensive estimates of the iron-ore reserves of the world, published during the summer of 1910 by the International Geological Congress in Sweden,' these Cuban deposits are estimated at about 2,000,000,000 tons. Certain it is that the reserve is a large one. The Spanish-American Iron Co., the Juragua Iron Co. (Bethlehem Steel Co.), the U. S. Steel Corporation, and others have been active in this exploration. The Spanish-American Iron Co. has established a port for the handling of these ores at Felton, has built a railway 16 miles to the ore-fields, and has operied up deposits for steam-shovel mining. Its expenditures have reached an aggregate of about $6,000,000 in preparation for the handling of these ores. Shipment of the ore to Sparrow's Point, Md., has begun and may be expected to rise to a considerable amount in the near future.

Jan 1, 1912

By John Henry Harden

WITH imperfect instruments it is impossible to make accurate surveys; the results are inaccurate maps, with their attendant consequences. The design of the writer is to describe an improved form of tripod head, and certain defects in an English transit and a miners' dial, with the method taken to remedy the defects of the transit. When the present transit superseded the surveyor's compass, there was one special objection brought against it, and with some show of reason ; namely, that the tripod of the compass with its ball and socket motion, allowed a quicker levelling-up (and, consequently, more work) than was possible with the transit. To this objection it was replied, that the ball and socket would not allow the instrument to be levelled with the same degree of precision that could be attained with the levelling screws, and that if time was sacrificed greater accuracy was attained. Nevertheless, it is a well-known fact that in this country, and especially in England, the compass or miners' dial holds its ground solely from its rapid adjustment. Ever since the introduction of the transit, efforts have been made to give to this instrument the same facility of levelling possessed by the compass or dial, and the same means have been tried, i. e., a . ball and socket motion, since a modification of this in some form was the only method that would answer. The upper part of a transit is, however, much heavier than the corresponding parts of a compass, and, therefore, requires more binding power, which cannot be ob¬tained with an ordinary ball and socket joint. It has been a study with instrument-makers to combine the facility of these two tripods -the quickness of the ball and socket with the steadiness and accuracy of the screws; but in all attempts in this direction the ball and socket of the compass has been literally followed, the entire stability of the instrument depending upon the friction of the ball in its socket. There is great need for a tripod that can be more easily manipulated than the present form, for it rarely happens that an engineer has a level surface on which to set his instrument, and very often

Jan 1, 1879

By C. R. Masson, M. L. Pearce

The nitrogen contents of seven specimens of iron and steel were determined by the three methods. Good agreement won generally observed between the results of the isotope -dilution and Kjeldahl determinations, tltzts establishing the reliability of the isotope -dilutzon technique. For some specimens, the vacuum-fusion values at 1650 °C were lower than the corresponding Kjeldahl values by up to 0.0015 pct absolute. These differences were eliminated for a specimen of "pure" iron by performing the vacuum-fusion analyses at 2100 ° to 2240 °C. The reason for this relatively high temperature required m the vaczium-fusion analyses is discussed. ThE determination of nitrogen in iron and steel has been the subject of numerous investigations and a concise review of the extensive literature in this field has recently appeared.' Two methods of analysis are most commonly employed, the vacuum -fusion and the chemical or Kjeldahl method. Except in special cases where the presence of certain alloying elements may present difficulties, both methods are generally regarded as applicable, although the vacuum-fusion method is more sensitive and is often preferred for samples of very low-nitrogen content. The method of isotope dilution, first employed for the determination of gases in metals by Kirshenbaum and Grosse,2 has recently been applied to the determination of nitrogen in iron and steel.3,4 The method is attractive in that it does not require the quantitative extraction of gas from the metal specimen. Staley and Svec3 modified the standard Kjeldahlpro-cedure by introducing, along with the steel sample, a measured amount of ammonium sulfate enriched in the isotope 15N. The nitrogen content was obtained by measuring the isotopic ratio 15N/14N in the resultant solution. The technique involved the distillation of nitrogen as ammonia from alkaline solution and subsequent oxidation of NH4+ in the distillate to gaseous nitrogen. The results for iron and steel samples of commercial origin were often in reasonable agreement with values quoted by the suppliers, although occasional marked discrepancies were observed, particularly with the results of vacuum-fusion analyses. Preliminary work in this laboratory4 on the determination of nitrogen by isotope-dilution in the gas phase yielded results for three samples which were significantly higher than the values obtained by vacuum-fusion. The present paper describes an extension of this work to a wider variety of samples. Analytical results by the Kjeldahl method are also reported. EXPERIMENTAL The technique employed for the isotope-dilution determinations was similar to that described elsewhere.4 Several minor modifications were made to the apparatus. These included the use of molybdenum instead of platinum-rhodium suspending wires when crucibles were degassed at temperatures above 1600°C. The circulatory system used previously for converting CO to CO2 was replaced by a single chamber, the walls of which were cooled directly in liquid nitrogen. Temperatures were measured with an optical pyrometer which had been recently calibrated and, as in the previous study, were minimum values obtained by sighting on the center bottom of the crucible. Temperatures obtained by sighting on the interior walls were always higher by 100' to 130°C with the design of crucible employed. Flat-bottomed crucibles exhibited an even larger temperature difference. To check the efficiency with which crucibles were degassed in the isotope-dilution apparatus, several experiments were done in the vacuum-fusion apparatus, suitably modified4 for isotope-dilution studies. Faster pumping speeds and higher degassing temperatures were possible, the latter due to the use of a generator with a higher power output (10 Kva at 398 kc per sec). In these experiments the combustion of CO was omitted and a correction4 was made for the contribution of CO to the ion current at m/e 28, used in determining the isotopic ratio R = l5NP4N. This correction did not seriously influence the re-

Jan 1, 1962

By S. C. Dhara

A process of solvent extraction and separation of platinum group metals (PGM) and gold using primary, secondary, tertiary, and quarternary organic amines has been briefly described. The effects of amine structures; the use of diluents; the principle of synergism and antisynergism in the mixed extractants; the oxidation states of metal ions are explained in the amine extraction process of precious metals.

Jan 1, 1984

By AIME AIME

THE second blast furnace of the Azov steel mill was blown in on Feb. 17, says the Economic Review of the Soviet Union. This furnace, the 111th in the U. S. S. R., has a volume of 930 cubic meters, and a daily output of 775 tons of pig iron. The 1934 program at the Azov plant includes three 250-ton-open-hearth furnaces, two coke-oven batteries, a repair shop, mine and agglomeration plant at Gamysh-Burum, and two ports, one at the latter town and one at Mariupol. On Feb. 21 the sixth open-hearth furnace of the Stalinsk (Kuznetsk) mill started operations; on Feb. 12 the fourth open-hearth furnace at the Liebknecht mill at Dniepropetrovsk, produced its, first steel, 47 tons of high-grade boring steel. The fourth open-hearth furnace

Jan 1, 1934

By L. K. Eigenbrod, F. Notaro

Enactment of Public Law 91-173 (Federal Coal Mine Health and Safety Act of 1969) has placed new responsibilities on the mining industry. The new law, aimed at eventually solving the problem of pneumoconiosis, sets new respirable dust standards at 2 mg per cu m. Techniques employed to date have been shown to lack total effectiveness in meeting the prescribed standards. Since it is possible that even the new standards will eventually have to be lowered to effectively attack the medical problem, the need for new and more reliable methods of assuring clean respirable air will intensity. This paper presents, in a preliminary manner, both the present technical capability and growth potential of cryogenic technology for supplying miners with clean breathing air. Work with two sizes of prototype supplied-air (cryogenic-liquid) respiratiors in Union Carbide's Fawn Coal mine, will be described. Other potentially fabricable systems will be discussed and a preliminary assessment made of the potential cost of introducing cryogenic air breathing systems in coal mine service.

Jan 1, 1972

By S. J. Rothman, J. J. Hines, D. Rokop, R. Bastar

Self-diffusion has been measured along each principal axis of mosaic-structured and relatively perfect a uvaniuln single crystals. The anisotropy reported before,' D[loo] = D[001] » D[010 , has been confirmed. and is shown to represent volume diffusion. Diffusion along the dislocations in the imperfect crystals increases the measured value of D significantly without changingr either the shapes of the penetvation plots or the anisotropy. SINCE a uranium is orthorhombic, the diffusion coefficients along the principal crystallographic axes need not be equal. A previous measurement of self-diffusion in three mosaic-structured a uranium single crystals1 showed that Dil00| =D[001 >>D[010 This result was deduced from penetration plots similar to those in Fig. 1. That is, the plots for diffusion along [loo] and [001] were the straight lines expected from the solution of the diffusion equation for the boundary and initial conditions of the experiment, while the plot for diffusion along [010] was curved so that the part near X = 0 had a much steeper slope than the straight lines did. The observed anisotropy could have been due either to volume diffusion or to diffusion along the very large number of dislocations in such crystals, according to the model proposed by aart.' The authors of Ref. 1 argued that the latter possibility was unlikely, but did not exclude it. To settle the question, a simultaneous measurement of self-diffusion in mosaic-structured and mosaic-free crystals was carried out. This paper reports the results, as well as a measurement of the temperature dependence of self-diffusion in a uranium. EXPERIMENTAL The single crystals of a uranium used in this experiment are listed in Table I, together with other experimental details. '(Mosaic structured" here means crystals grown by solid-state phase change.3 The Laue spots from such crystals spread over about 6 deg of arc, which indicates that the density of dislocations is very large. "Perfect" crystals are ones grown by Fisher's grain-coarsening tehnique; the Laue spots from these are quite sharp,4 which shows that the dislocation density in these crystals is much lower. All of the crystals were made from high-purity uranium; a typical analysis is given in Ref. 1. The actual diffusion directions were within a few degrees of the nominal. The thin layer-sectioning method was used. The experimental techniques were similar to those described in Ref. 1, except the sectioning. Crystals Za, 2b, 2c, 4a, 4b, and 4c were sectioned on a lathe. Crystals 3a, 3b, and 3c were sectioned by grinding on glass plates, with 1 p diamond powder in butyl alcohol as the abrasive. The use of glass plates eliminated the crowning noted in Ref. 1, and the use of butyl alcohol as a lubricant simplified the chemical processing of the sections. Material from the sides of these three crystals was removed by spark machining before sectioning. The sectioning of crystals 4a and 4c was botched. A small cylinder of metal was extruded from the center of crystal 4a while turning off material from the side of the sample. Crystal 4c was misaligned by 2.1 x 10"3 cm because the dial gage jammed during the alignment. Notwithstanding these errors, useful data were still obtained from these crystals. The points

Jan 1, 1967

By D. H. Forbes, I. B. Cadoff, H. M. Manasevit

Single-crystal silicon films have been obtained on several natural crystal faces of BeO using the thermal decomposition of silane and the hydrogen reduction of silicon tetrachloride. From an analysis of X-ray diffraction data it was determined that the following film-substrate orientation relationships exist: (111) Si 11(0001) BeO, (111) Si 11(1011) BeO, (100) Si 11f1010) BeO. and (110) Si 11(1010) BeO. An analysis of the crystallographic relationships between the film and substrate indicates that a match occurs between the silicon atoms in the film and the berylliuni ion sites in the substrate. This correspondence is in agreement with previous work on the deposition of silicon on sapphire.1-3 silicon on spinel: and tungsten on sapphire. The high resistivity, thermal conductivity, and radiation resistance of beryllium oxide make it an important substrate material for the deposition of thin films of silicon or other semiconductors. The importance of semiconductor-insulator composites to the field of integrated microelectronics has been well-documented in the case of silicon on sapphire.'-' The successful growth of large-area single-crystal silicon on an insulator, sapphire, was first reported in 1963.1,2 Since that time studies have been made of the crystallographic relationships between the deposited film and the sapphire substrate. On the basis of the observed relationships, a model has been proposed relative to the crystallographic requirements for epitaxy between the semiconductor film and the metal oxide substrate.3 It is proposed in this model that epitaxy is the result of a match between atoms of the deposited film and the metal ion sites of the substrate plane. This match is not limited to a 1 to 1 correspondence between sites in the two lattices. Sub- sequent studies of the deposition of silicon on spinel4 and tungsten on sapphire5 have yielded data which support this model. On the basis of this previous work it was felt that silicon on BeO should also fit this model. In the present study, the choice of substrate orientation was limited to the natural faces of synthetic BeO crystals. Of the faces available, the (0001) plane seemed the most favorable for epitaxial growth. EXPERIMENTAL PROCEDURE Silicon films were deposited from silane and silicon tetrachloride in the apparatus shown in Fig. 1. The hydrogen ambient gas was purified by passage either through a DEOXO unit, molecular sieves, and a liquid nitrogen cold trap, or through a heated Pd-Ag thimble. The gas was then mixed with the silicon source materiai and passed over the substrate which lies on a spacer above an inductively heated silicon pedestal. The following deposition conditions were used: a hydrogen flow rate of 3 liters per min with silane and silicon tetrachloride concentrations of 0.2 mole pct and a pedestal temperature of 1175" * 5°C as observed with an optical pyrometer assuming an emissivity of 1.0. Deposition was preceded by a 15- to 30-min hydrogen-etch period conducted at a temperature of 1275°C (obs). Adherent silicon films from 2 to 10 u were grown on the various BeO faces. The substrates were synthetically grown beryllium oxide single crystals ranging from 5 to 10 mm in

Jan 1, 1967

By D. T. Peterson, F. A. Schmidt, J. D. Verhoeven

The velocity of mig-ration of these solutes in thorium metal due to a high amperage dc current was measured at several temperatures. All three solutes migrated in the same direction as the electron flow. Diffusion coefficients were combined with the migration velocities to predict the steady-state concentration profile. Electrotransport was shown to be an effective method of removing carbon, oxygen, and nitrogen from thorium and resistance ratios several times larger than for crystal bar thorium were achieved. However, the maxirnum attained purification was well below the predicted values, apparently due to some form of contamination. THE migration of solutes in metals when a high current density dc current is passed has been known for many years. This phenomenon has been the subject of a number of reviews published in recent years.l~* Many of the earlier investigators of electromigration of interstitial solutes interpreted the direction and velocity of migration on the basis of a charge on the solute particle. This interpretation is unclear because, in a given experiment, one cannot separate the contributions to the force moving the solute which arise from the charge on the solute in an electric field gradient and the momentum transfer from the scattering of the electrons or holes. There have been only a few quantitative measurements of interstitial migration velocities and some of these have been characterized by poor accuracy or by errors in the analysis of the experiment. The electrotransport mobilities of carbon, nitrogen, and oxygen in thorium were determined by observing the rate of movement of a discontinuity in the concentration profile. This method was used by Carlson el a~.~ to determine the mobilities of interstitial solutes in yttrium and its advantages are discussed in that paper. The specimen is essentially a pair of semi-infinite, bar-type diffusion couples. The electro-transport velocity was measured by observing the displacement of the mean concentration point in a measured length of time. The diffusion coefficients were calculated by the Grube method from the concentration profile. The transport mobilities and diffusion coefficients can be used to predict the concentration profile in an electrotransport experiment of a given time, current density, and specimen length. At long times a steady state will be reached such that the natural logarithm of the concentration of each solute varies linearly along the bar with a slope which is equal to the velocity of the migrating solute divided by its diffusion coefficient. The estimation of the purification potential of electrotransport is discussed by ~erhoeven.' A comparison of the concentration profile and the purification which should be expected from known solute velocities and diffusion coefficients with that which is obtained in an experiment can be very useful in indicating whether the maximum possible purification has been achieved. EXPERIMENTAL METHOD The apparatus used in this study consisted of a sample chamber which was equipped with two electrodes, a sight glass, and a flange for mounting to a high-vacuum system capable of obtaining pressure of 2 x lo-? Torr. The chamber was made of stainless steel and was 4 in. in diam and 6 in. long. The seal between the electrodes and the chamber was made with "0" rings and compression bushings. The thorium specimens were threaded and screwed into tantalum "U"-shaped adapters attached to the ends of the electrodes. This arrangement is shown in Fig. 1

Jan 1, 1967

By F. W. Luersson

High carbon, low phosphorus steel can now be made from pig iron containing 0.7 pct P or more, in a commercial sized open hearth furnace. No external heat is required for refining, and steel produced is identical with basic open hearth steel. THE classical Thomas process, which requires liquid pig iron containing over 11/2 pct P, yields a product relatively high in phosphorzs and nitrogen. Unless large quantities of recarburizers are added to the refined steel, the product is low in carbon content. Thus, the Thomas process is not well suited to American raw materials, and its product is often not acceptable according to the standards set by American industry. The shortcomings of the Thomas process have long been recognized; with the advent of low cost oxygen, studies were initiated to develop pneumatic processes which would conceivably overcome the inherent objections to Thomas steelmaking. Several such modified basic pneumatic processes have been tested experimentally in commercial trials during the past decade. Probably the most widely publicized of these developments has been the oxygen converter process as practiced in Austrial,2 and in Canada.8 n this process, oxygen is substituted for air and introduced above the liquid bath in order to increase the heat available to the metallurgical system. This avoids the need for high phosphorus raw materials and gives a product low in nitrogen. In this process, the phosphorus content in the final product depends, to a considerable extent, on the total amount of that element in the burden. The rotary furnace4 which is now in commercial operation at Domnarvet Steelworks, Sweden, is producing low phosphorus steel from iron containing 1.8 to 2 pct P. One or more early slags are removed and by this means high carbon steels of open hearth quality can be produced. At this stage of development there is some question as to the applicability of the rotary process to large heats. Another development has been the use of oxygen in combination with either steam6 or carbon dioxide yn the basic bessemer, thus avoiding the introduction of nitrogen gas into the refining system and giving a product relatively low in nitrogen content. A double slag process has been used in Europe7 in conjunction with a regular Thomas converter, by means of which it is possible to obtain a phosphorus content in the product approaching that obtained in basic open hearth steels. The Turbo-Hearth process:' which uses the side blowing principle so as to produce low nitrogen steel from normal American pig irons, has been developed experimentally in this country. A process fitted to U. S. raw materials All of the preceding processes, with the exception of the rotary furnace, suffer from the common shortcoming that they cannot be adapted to the production of high-carbon, low-phosphorus steels unless large proportions of recarburizers are added. In 1947, a program was initiated by the Inland Steel Company1' to study an oxygen steelmaking process specifically designed to utilize the full range of phosphorus analyses encountered in American pig irons and to give finai products with phosphorus and nitrogen contents comparable to steel produced by the basic open hearth process. Some of the objectives of the proposed process are: 1) the process should be able to accommodate molten pig iron conta;rl;rrg up to 1 pct P., 2) sne process should be subject to close control of carbon analysis, 3) the process should be capable of producing high carbon

Jan 1, 1958

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring's predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,' who applied Eyring'sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann's constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers' data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

Long range expansion plans begun in 1966 by The International Nickel Co. of Canada, producer of over 50% of the free world supply of the white metal, are so mammoth as to give rise to the speculation that something might have to burst at the seams. From an annual level of capital expenditure of $35 to $70 million, the company jumped in 1967 to $145 million in new capital investment and will come close to $200 million in 1968. Inco expects to spend $700 million in the next five years, beginning in 1968, for new mines and surface facilities in Canada. The program involves the opening of nine new mines within the next 3 1/2 years, expansion of producing mines, and construction of new plants and modernization and expansion of established ones to process the increased ore production. Beyond this, the company is committed deeply in developing new sources of nickel abroad. Any one of these new projects, if proven economic, would necessitate expenditures of about $100 million or more. For Inco, the economic strain was relieved without a rupture this spring when Henry S. Wingate, company chairman, reported' at the stockholders annual meeting that $150 million had been raised by the sale of bonds. This marked the first time in 32 years that the company had gone into debt.

Jan 10, 1968

By William P. Blake

This camp is just now startled by the alarming suggestion that unless there shall speedily be an appreciation in the value of silver, and a decrease in the cost of salt, it will be prudent business policy to close the Alice mines and mills until the conditions of production are more favorable. Such an event would be a great blow to the prosperity of Butte. It would throw some hundreds of men out of employment, and it might lead to the adoption of the same policy by other companies, which, like the Alice, have not been able to pay dividends to their shareholders for a long time. The question arises, and becomes emphatic: If, under the present adverse conditions, the mines and mills cannot be made to pay a proper profit, why should they continue to be worked ? The owners mentally ask: Shall we go on exhausting our mines, pouring out a stream of silver for the maintenance of the community, and the support of the rail ways, or shall we husband our reserves, withdraw the miners from our slopes, and wait for more favorable conditions ? This is the impending question, and all concerned dread to meet and answer it. Let us briefly review the situation and forecast, if possible, what the solution of' the problem will be. It must be understood that the discussion does not include, or refer to, the immense copper-producing interests of the camp, which may or may not be upon a very much more satisfactory basis. It will be confined chiefly to the operations of the Alice company, sta tistics of which are at hand, without involving the other silver com panies in the conclusions beyond those inevitable from well-known facts, patent to all. There are at present in Butte and in its vicinity in the principal mills an aggregate of 290 stamps dropping upon silver-ores: Alice,...........80 stamps. Moulton,. .........40 " Lexington,...50 " Silver Bow,.........30 " Blue Bird,..........90 " The Alice mills at present, with their 80 stamps, devour, in round numbers, from 100 to 120 tons a day. The actual amount

Jan 1, 1888

By F. W. Jr. Sperr

THE byproduct coke oven is the most important artificial source of fuels for metals melting. Its products are solid, liquid, and gaseous in form. The amount of coke and primary byproducts obtained per ton of coal varies with the nature of the coal. The following represents the results obtained in many plants: Metallurgical coke (over 3/4 in.) 69 per cent. of coal Domestic coke (1/2 to 3/4 in.) 2 per cent. of coal Breeze (under 1/2 in.) 4 per cent. of coal Surplus gas, cubic feet per net ton 6600 Gas for heating ovens, cubic feet per net ton 4400 Tar, gallons per net ton 9 Ammonium sulfate, pounds per net ton 25 Benzols, gallons per net ton 4 All of these products, except ammonium sulfate, have important fuel value. Part or all of the metallurgical coke may be crushed or screened to furnish additional domestic coke. If producer gas is used, there will be a surplus of 11,000 cu. ft. of coke-oven gas per net ton of coal. The use of coke in the metallurgical industries has been retarded by the mental attitude of writers who disregard the dependence of coke quality on the conditions of its manufacture. Terms like "byproduct coke,"' "beehive coke," "48-hour coke," and "72-hour coke" are only generally descriptive and tell nothing of the coke quality. For example, one writer1 stated that in brass-foundry practice, Connellsville coke is considered much superior to byproduct coke on account of the high sulfur content of the latter. Another2 says, "At equal prices for hard Connellsville coke and for byproduct coke at the foundry door, the hard coke is unquestionably cheaper. It will melt more metal per ton than the byproduct coke and requires less labor, as the byproduct coke is less dense and burns faster, thus requiring more frequent firing." A little study of the conditions under which coke is manufactured will show the error in mak-

Jan 10, 1920