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By J. R. Long, R. S. Dean, F. S. Wartman, E. T. Hayes

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946

By Louis G. Bailey

This paper .reviews some of the key developments which have been made in the synthesis of the III-V compound semiconductors and the associated progress in obtaining high-quality material for device development. The history of the investigation of the semi-conducting properties of these materials has indicated the need for synthesis techniques capable of producing rnaterial of high chemical purity and physical perfection. The progress in the area is described, and the present status of quality of several compounds is discussed. In addition, recent studies of localized epitaxial deposition of GaAs into semi-insulating GaAs substvates for the development of arrays of devices ave reviewed. In conclusion, some important areas for future research and developrnent are discussed. INTEREST in III-V compounds as semiconductors dates back to the period 1950 to 1952, when Goryunova, Ioffe, and, in particular, Welker determined that 111-V compounds were structural analogs of the group IV elements carbon, silicon, germanium, and tin and that they were also semiconductors.'-3 Since that time interest in the properties of these materials has ex- panded rapidly. During 1953 and 1954, the first reports of rectification, photoconductivity, and optical absorption in these materials came from several investigators. In 1955, recombination radiation from samples of GaAs, InP, and GaSb was reported by ~raunstein .' This radiation was produced by injected minority carriers from point and large-area contacts. From 1955 to 1960, efforts increased on preparing large, pure specimens of these materials for the study of basic physical phenomena and device exploration. By 1960, materials preparation and the understanding of the physics of some of the materials had advanced to where some very interesting and potentially useful phenomena came under study. The first observation of electric-field-induced changes in the optical absorption edge (Franz -Keldysh effect) of 111-V compounds was reported for GaAs by Moss in 1961.' In 1962 the study of recombination radiation advanced rapidly. Keyes and Quist6 and Pankove and Berkey-heiser7 reported high radiative efficientices obtained from recombination, and then the first injection electroluminescent lasers in GaAs were announced by Hall ef al.,' by Nathan et al.,O and by Quist ef al.,'O and in Ga(As, P) alloys by Holonyak and Bevacqua." Hil-sum has reviewed the early work leading to the first observations of laser action in GaAS." Recombination processes in GaAs, Gap, and the other 111-V com-

Jan 1, 1968

By W. P. Sykes

THIS investigation was undertaken primarily to establish the relations existing between temperature and mechanical properties in molybdenum, nickel, and an aluminum-copper alloy. Molybdenum (m.p. 2500° C.) was chosen because it is partly similar to tungsten and partly similar to the common ductile metals. Also it is known to furnish, by proper treatment, a desirable material to use in studying relation of grain size and physical properties. The molybdenum used was of the quality that is drawn into wire 0.003 in. in diameter for use as filament supports in incandescent lamps; chemical analysis shows less than 0.1 per cent. of impurities. Nickel belongs to the same class as iron. Its melting point is 1450° C. and an allotropic change at about 370° C. results in a loss of magnetism above that temperature. This feature made nickel doubly valuable for the purposes of these tests. The nickel used was obtained from the Driver-Harris Co. as 0.090 in. (2.3-mm.) wire, annealed; analysis showed 99.8 per cent. nickel and 0.150 per cent. iron. Aluminum is one of the low melting-point metals. Some tensile tests at elevated temperatures have been reported by Bengough but the possibility of learning more with the low temperature and sensitive apparatus available recommended this metal. The samples marked Al are an aluminum-copper alloy; they contained 3 per cent. copper, 0.42 per cent. iron, and 0.21 per cent. silicon. The presence of the copper somewhat complicates the analysis of the results; but the action of copper in aluminum has been studied so that its influence might have been foretold, in part at least. The material and analyses were furnished by the Aluminum Castings Co. The nickel wire, which was deformed at 400° C., was drawn under a bath of molten lead and through a die, which also was immersed in the bath. A thermocouple was suspended in the molten metal to indicate

Jan 1, 1921

By K. Barron

"A computer program is described which will analyze the stability of coal pillars. The extent of the peripheral failed zone and the central elastic core of the pillar, the stress distribution across the pillar and its strength can be determined by a ""sliceby- slice"" analysis technique. The program incorporates a brittle/pseudo-ductile transition point so that a pillar may fail by brittle fracture or pseudo-ductile yield. It is shown that:(i) There is a minimum pillar stress below which fracture cannot initiate; hence there is a minimum pillar strength. (ii) In specific circumstances (narrow pillars) , once fracture initiates at the pillar edge it must propagate immediately to the pillar centre. This unstable situation is called ""catastrophic"" failure and might be regarded as a model of a pillar ""burst "". (iii) For wider pillars, the failed zone ex tends gradually into the pillar as the loading increases until it reaches the pillar centre when the pillar is deemed to have f ailed. This is called the point of ""ultimate"" failure.The critical pillar widths to avoid catastrophic and ultimate failure can be calculated.A hypothetical analysis of five rib pillars is given to illustrate the application and the results obtained from the model. The model is then used to analyze three case histories taken from the literature. The first demonstrates the applicability of the brittle/pseudo-ductile failure criteria for Pittsburgh coal. The second compares the pillar strength formulae derived here with those of Salamon and Munro(13) and Bieniawskiou . The final case history compares the model analysis with field stress measurements in a yielding pillar. In all cases the model results are compatible with the case histories."

Jan 1, 1984

By Robert D. Brown

"The Conservative Government 's budget proposals brought forward on December 11, 1979 have been withdrawn, but they are far from dead. On the contrary, a number of those budget proposals, especially the ones which would close loopholes and result in other technical changes being made to the Income Tax Act, should be considered to be alive and well.It is not unreasonable to expect the next government, of whatever political persuasion, to reintroduce many of these technical changes in the next federal budget. For that reason, last December's budget may have offered an interesting preview of what the mining industry and other taxpayers can expect in 1980. It is quite possible that some of these changes may be effective as of the original dates announced in the withdrawn budget proposals.This month, ""Tax Notes"" reviews the main pro visions of Mr. Crosbie's December, 1979 budget, with a primary focus on the changes that would have affected the resource sector.It must be emphasized that all of the budget proposals discussed herein have been withdrawn, that none of them are law and that any actual changes in our tax rules will have to be dealt with by the new Parliament that will be assembled following the February 18 election. December 1979budget withdrawnThe federal budget proposals brought forward by Finance Minister John Crosbie on December II, 1979 were withdrawn as a result of the defeat of the Conservative Government on a motion of non-confidence in the House of Commons on December 13. However, it appears quite possible that at least some of the proposals may be introduced into Parliament at a future date, possibly with retroactive effect.In a press release issued by the Department of Finance, Finance Minister John Crosbie stated that if the Conservative Government is returned to power, it will reintroduce all of the measures contained in his December II budget.Mr. Crosbie stated that all of the income tax measures contained in the budget would be reintroduced, effective on the dates indicated in the Notice of Ways and Means Motion tabled on December II. Some of the more important measures in December II budget, and their effective dates as indicated in the Notice of Ways and Means Motion, are discussed below.The December budget had also introduced or increased excise taxes or duties on gasoline, wines, cosmetics and photofinishing. If the Conservative party is re-elected, these measures will be reintroduced with prospective effect (i.e . effective as of new dates to be announced in the new budget)."

Jan 1, 1980

By Harold R. Kokal, Madhu G. Ranade

A metallurgical/flux is a substance that is added to combine with gangue (unwanted minerals) during ore smelting, with impurities in a molten metal, or with other additives in metal refining processes to form a slag that can be separated from the metal. Because slags are immiscible with the metallic melt and are of lower density, a separation of the slag and metal occurs if the viscosity and surface tension are of the proper values. The chemistries of slags are adjusted to provide the proper melting point, viscosity, surface tension, conductivity, specific heat, density, or chemical properties to effect the desired task. In addition to absorbing impurities from the metal, the purposes of the slag are to thermally insulate the metal bath, protect the molten metal from the atmosphere, and control the chemical potential of the system. Several excellent references on slags and metallurgical fluxes are available (Boynton, 1980, Lankford, Jr., et al., 1985, Turkdogan, 1983, Rosenqvist, 1974, Fine and Gaskell, 1984). The function of the slag might vary at different stages within a process prior to final melting. For example, the slag composition and behavior will change as materials descend in the iron blast furnace, or as they melt in the early stages of formation of steel- making slags. Selection of the chemistry for a slag might be influenced by factors outside the primary function as when blast furnace slags are used to make cement, rock wool insulation, or fertilizer supplements. Sometimes slags contain a sufficient amount of valuable recoverable elements to be sold as raw materials for other processes. Fluxes are often referred to as acid, basic, or neutral. Acid fluxes are those that generally form acids in water and bases are those that would generally form bases in water. Typical acid fluxes are silica, alumina, and phosphorus, although alumina can function as either an acid or base. Typical basic fluxes are lime and magnesia. Fluorspar, or calcium fluoride, is a neutral substance because it can be viewed as the reaction product of a base and an acid. The degree of acidity (ratio of acids to bases) or basicity (ratio of bases to acids) is often specified to characterize the slag chemistry for a particular system. The system might also be referred to as acid or basic depending on the choice of slag, for example, basic steelmaking uses slags with more bases (lime and magnesia) than acids (silica and alumina). Many forms of minerals and compounds have been used as fluxes depending on the process requirements, availability, costs, requirements for recycling of intermediate products, and environmental concerns. Because slags are most often mixtures of oxides and silicates, fluxes are usually oxides, carbonates (which decompose to oxides) and silicates. Slags comprising phosphates, borates, sulfides, carbides, or halides have also been used (Rosenqvist, 1974, Moore, 1981, Szekely et al., 1989). In ironmaking and steelmaking, some acidic components are sometimes added. In nonferrous processes slags and fluxes are acidic with silica as the primary component, and although the use of basic flux such as limestone or lime is not extensive, some amount is used to modify slag properties and some refining slags are lime based. The production of iron is accomplished by smelting of ores, pellets, and sinter in blast furnaces with subsequent refining of molten iron and scrap in oxygen-blown processes. The electric furnace is used to make steel, stainless steels, ferroalloys, and special alloys, whereas ferromanganese is often made in blast furnaces. Fluxes are used in all of these processes, and either limestone or lime is the major flux component with some dolomite, dolomitic lime, silica, alumina, and fluorspar being used. In ironmaking, the flux is added either by direct charging or through sinter and fluxed pellets. In steel refining by the basic oxygen process, flux is added as lime and dolomitic lime that are either charged as lumps or injected as fines. Some small amount of limestone is sometimes used. Fluorspar is often added as lumps or mixed with other fine materials in briquettes. Alumina is sometimes added to blast furnaces either by direct charging of sized lumps or through sinter. Typical acid fluxes are sand, gravel, quartz rock, used silica brick, or raw siliceous ore (Lankford, Jr., et al., 1985). Olivine, which is a magnesium-silicate mineral, has been added to iron blast furnaces to enhance removal of alkalis (Lankford, Jr., et al., 1985). Alumina in the form of bauxite, aluminiferous clay, and recycled alumina brick has been used as flux. Alumina can function amphoterically as either an acid or base, for example it can form aluminum silicate in high silica slags or calcium aluminate in lime-bearing slags (Lankford, Jr., et al., 1985). Limestone (calcium carbonate) and dolomite (magnesium-calcium carbonate), or fluxstones as they are sometimes called (Boynton, 1980), and their calcined forms, lime and dolomitic lime are the major basic fluxes. In the latter cases, the carbonates are de- composed in a kiln-type process to drive off carbon dioxide that might otherwise interfere with the subsequent smelting or refining process or require expensive forms of energy to effect the decomposition (e.g., by combustion of coke in the iron blast furnace). Limestone is considerably less expensive than lime because it is not calcined; however, lime is far more difficult to handle and reacts readily with water. Dolomite and dolomitic lime are used for their magnesia content. Fluorspar is a neutral flux often used as an additive in steel- making slags to improve fluidity, but it has also been used in combination with lime as a primary slag in electroslag refining (Duckworth and Hoyle, 1969). Fluorspar is available in several grades, with the lowest grade often used for steelmaking. When the price of fluorspar has risen, substitutes including aluminum smelting dross, borax, manganese ore, titania, iron oxides, silica sand, and

Jan 1, 1994

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By Janet Briggs, Michael Vertes, J. F. Shirley, R. E. Cutherbertson, Alexander Sutulov, J. D. Vincent

Molybdenum, the 42nd element in the periodic table, is now a very important metal in industry of the United States and the world. Chemically, it is a very complex element having valences of 0, +2, +3, +4, +5, and +6, and can exist as a mixture of these valences in many compounds. It was discovered and separated by Scheele in 1778. At the present time, molybdenite is the only important commercial source of molybdenum. Molybdenum occurs in some 12-14 different recognized minerals, but practically all of the production is molybde¬nite. As late as 1915, it was considered a rare metal. Germany made extensive use of it during the first world war, which resulted in the establishment of a molybdenum industry in the United States at Cli¬max, Colo., in 1917. It was not until the mid-1920s when its introduc¬tion to steelmaking developed for the US automobile industry that the metal gained important acceptance. The first notable example was the Willis-Saint Claire automobile introduced in 1921 by C. Harold Willis, formerly chief metallurgist for Ford Motor Co. Molybdenum has also been produced in the US from wulfenite (PbMoO4) from Arizona and Nevada, and a small amount of molyb¬denite was produced up to the early 1970s as a coproduct from two molybdenum-bismuth mines in Quebec, Canada. The first byproduct production of molybdenite from a copper con¬centrating operation was achieved at Cananea, Sonora, Mexico, and was followed shortly by the Utah division of Kennecott Copper Co. in the mid-1930s. This section of the Handbook is divided into four main subdivi¬sions: Chapter 2, which deals with the concentration and recovery of molybdenite from primary molybdenum ores; Chapter 3, which deals with the recovery and separation of molybdenite as a byproduct from copper production; Chapter 4, which deals with the conversion practices employed for converting molybdenite to the oxide or metal form; and Chapter 5, which covers the uses of molybdenum in steel¬making, chemicals, pigments, lubrication, catalysts, etc. The Free World molybdenum production, for the past eight years from all sources, is shown in Table 1. 2. Primary Molybdenite Ores General In 1978 there were four primary molybdenite recovery plants in operation: Climax, Endako, Quests, and Henderson. For over half a century the Climax mine has been by far the largest and most important source of molybdenum in the world. During the early 1970s a few primary molybdenite mines in British Columbia were shut down due to adverse economical conditions. The largest of these was British Columbia Molybdenum, formerly owned by Kennecott Copper Corp. The Climax plant and operations are described in detail and the opera¬tions of the other plants are summarized following a general discussion of recovering molybdenite from primarily molybdenite ores. Recovery of molybdenite as a byproduct will be taken up in Chapter 3. Geology Molybdenite production from mines in which it is the sole or preponderantly important mineral is confined to ore bodies in granites or igneous-type rocks or pegmatite dikes. More than one state of mineralization is sometimes present as at Climax, York, Hardy, and Questa. In the case of Climax, important byproduct recovery of tung¬sten, tin, pyrite, and monazite is also attained. The molybdenite is commonly disseminated very finely in the siliceous granitic gangue but does occur in stringers and blebs in silicified mineral solution channels. Treatment of Primary Molybdenum Ores All primary molybdenum ores are low in molybdenite, the content ranging from less than 0.20% MoS2 to a high of about 0.40% MoS2. A high resistance to grinding is a common ore characteristic combined with a habit of very fine dissemination of molybdenite in the siliceous portion of the ore. Because of low MoS2 content, high hardness, and fine dissemination of molybdenite in primary ores, it has been necessary to develop a special mill treatment which yields an accepta¬ble recovery at a reasonably low milling cost. Essentially, the treatment consists of intensive rougher flotation at a relatively coarse grind with production of a low grade rougher froth containing a substantial percentage of the molybdenite in the form of low grade middling particles, followed with multistage regrinding to liberate the locked molybdenite and several stages of flotation cleaning to produce a finished grade concentrate. Rougher flotation on pulp ground to ap¬proximately 35 mesh is common practice, even if complete liberation of molybdenite from siliceous gangue may require regrinding to 200 mesh. The flotation of middling particles with a very low content of molybdenite in the rougher flotation step has been made possible by the application of a combination of reagents first developed at the Climax mill and used with some modification in the treatment of all primary molybdenum ores. The reagents commonly employed and their functions in flotation are:

Jan 1, 1985

By Palmer W. T

The successful re-opening of the Cobar min- eral field was dependent upon the success- ful introduction of highly productive, low cost mining. Mechanised cut and fill stop- ing with incline access was selected for the C.S.A. mine because it permitted flexi- bility, complete primary extraction with no secondary pillar recovery, minimised dilu- tion and oxidation, a minimum of pre-pro- duction development and because diesel powered load-haul-dump (L.H.D.) units were proving reliable and highly productive in the U.S.A. Although L.H.D. vehicles are the key to the success of the mining method, four other main groups of vehicles are utilised in the mine - trucks, scaling vehicles, ser- vicing vehicles and specialist vehicles. The operating requirements at the C.S.A. mine are more stringent than those encount- ered in many other underground mining oper- ations. The first L.H.D. vehicle used at Cobar - the Transloader - had considerable difficulty in loading and discharging coarse production ore. The Wagner ST5 Scoop Tram performed this duty much better. However, the first generation Scoop Trams were not robust enough to withstand the heavy duty and many modifications were necessary before acceptable availabilities were obtained. Similar modifications were necessary for the Eimco 916 vehicle but the Eimco 915 unit came much closer to meeting the duty requirements. Eventually Cobar technical personnel design- ed a L.H.D. vehicle to meet specific C.S.A. mine conditions. These units have proven most satisfactory. Over 8 years of operation the underground vehicle fleet has become a proliferation of vehicle types. A standardisation pro- gram has been initiated based upon common prime movers being mated with "trailer" units to serve specific functions. Standardisation will reduce inventory levels and facilitate training of operating and maintenance personnel.

Jan 1, 1973

By Mallett CW, Hammond RL

Geological maps of the Pacific Rim recently published by the Circum-Pacific Council for Energy and Mineral Resources have provided a useful perspective from which to view modern plate interaction and the evolution of modern fold belts. An important lesson from any study of modern plate interaction is that of the normality of change. The chaotic is more usual than the simple. Present day convergent margins with mixed characteristics are measures of this chaos. Indeed, the character of less than one third of the present length of the Pacific Rim can be ascribed to conventional models of plate interaction. Another lesson is that of the great mobility of oceanic crust. Enormous areas of the Pacific may not be represented in future fold belts developed at convergent boundaries unless normal consumption processes are disrupted, and even then only by linear zones a few kilometres wide. The axes of divergent boundaries creating Pacific Ocean crust have been equally mobile, with new spreading sites taking over from older sites through time. Divergent boundaries, whether active or inactive, consist of oceanic crust, and may be wholly consumed at collision sites with convergent boundaries. Their only potential contributions to fold belt evolution are transforms and magmatic activity. It is this transform component that can provide us with a mechanism to explain the apparent contradiction of both compressional and extensional features occurring together in a developing fold belt. Reconstructions for the SW Pacific are used to demonstrate that the fold belts under construction during the last 4% (Jurassic- Recent) of geologic time have involved interaction between convergent, divergent, and transform boundaries. In the last 15% of earth history (Late Proterozoic-Recent), many enigmatic features of the geologic landscape in Eastern

Jan 1, 1987

By A. U. Seybolt, J. L. Walter

The effects of the addition of 0.5 pct ThO2 (by volume) on the grain structure and texture of heavily rolled tungsten sheet were studied. Powder metallurgy ingots were rolled to sheet, 0.001 in. thick, and samples were annealed at temperatures from 1200" to 2500°C. The heating rate to the anneal temperature was varied from 3°C per min to 6500°C per min. The orientations of the largest grains were determined by X-ray diffraction. The disposition and loss of the ThO2 particles were determined by electron transmission microscopy and the activation energy for remozlal of the thorium was measured by mass spec-troscopy. Heating rates below about 800 C per min produced large, highly elongated grains. Higher heating rates produced much smaller, less elongated grains. The grain structure and texture of the slowly heated samples were identical to the structures and textures of heavily rolled tungsten foil conventionally doped with aluminum, silicon, and potassium but the recrystallization temperature was about 200°C lower. There was stringer-like dispersion of larger ThO2, particles superimposed on a uniform dispersion of fine particles. The particles increased in size and decreased in number with time at temperature. The loss of particles was accompanied by formation of grain boundary voids and surface pits. The activation energy for removal of the ThO2 was about 40 kcal per mole. THE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of heavily rolled sheet1 or drawn wire."4 Thus, "doped" tungsten sheet, rolled to 0.001 in. and recrystallized, develops a structure consisting of large, highly elongated grains of a specific preferred orientation.' It has been shown that the elongated grain structure was caused by a dispersion of particles, identified as mullite (Al6si2O13),1,4 in strings parallel to the rolling direction in sheet or to the wire axis. Identical results were obtained for iron which was doped with glass and rolled to 99 pct reduction of thickness and recrystallized.5 Again, the glass particles were disposed in strings parallel to the rolling direction. The strings retarded boundary migration in the lateral direction but grain growth was able to proceed relatively unhindered along the direction parallel to the strings.1,5 In both the doped tungsten and the glass-doped iron, the particles were highly plastic during the high-temperature deformation. Since mullite melts at about 1800°C and the glass employed melts at about 810ºC, the particles were probably molten during the recrystallization anneals (above 1800°C for the doped tungsten and 850°C for the glass-doped iron). There are indications in the literature that particles not plastic at hot-working temperatures (up to about 1550°C for tungsten) may also impart elongated grain structures by primary recrystallization of worked alloys. Examples are dispersions of tantalum carbide in chromium,6 and ThO2 in nickel where elongation ratios of recrystallization grains of up to 20:l were obtained.7 Strings of ThO2 particles in W-ThO2 wire have been seen by Rieck.8 In view of the available evidence, it was of interest to extend the previous studies of doped tungsten and glass-doped iron to include W-ThO2 sheet materials. Of specific interest was the grain structure, preferred orientation, recrystallization temperature, and disposition of the thoria particles. EXPERIMENTAL PROCEDURE A) Material Preparation. About 380 g of blue tungsten oxide (approximate composition WO3) was wet with a sufficient amount of aqueous solution of Th(N03)4 to provide 0.5 vol pct ThO2. The wet mixture was stirred to distribute the doping material uniformly throughout the powder. Stirring was continued while the mixture was heated until it was completely dry. The dried, doped mixture was then reduced to tungsten powder by heating at 850°C for 2 hr in a stream of dry hydrogen. The doped tungsten powder was hydropressed in a rubber sack at pressures of 50,000 psi to produce an ingot approximately 2 cm diam by about 5 cm long. Next, the pressed cylinder was heated in hydrogen for 2 hr at 1350°C to render it strong enough for machining. The cylinder was machined to a square cross section of 1.6 by 1.6 cm with rounded corners. Finally, the bar was heated for 2 hr at 2150°C in hydrogen to provide a sufficiently dense mate rial to withstand the hot-rolling operation. Prior to rolling, the ingot was reduced in thickness by about 20 pct by forging at 1550°C. This served to increase the density of the material and to widen it slightly for better rolling characteristics. The forged ingot was then rolled at 1550°C to a reduction of 45 pct of thickness, following which the rolling temperature was reduced to 1300°C and the slab rolled, with several reheats, to 0.050 in. Further reduction was accomplished at 800°C in tungsten sheet packs to a total reduction of about 99.85 pct. B) Annealing Treatment and Observation of Structure. Small samples of the rolled foil were annealed in one of two ways. Some of the samples were suspended in a covered tungsten can and annealed at temperatures from 1200" to 2200°C for various times in vacuum of l0-7 to 10-6 mm Hg. The can was heated by induction and temperatures were determined by optical pyrometry

Jan 1, 1970

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By Bobby G. Cahoon

The ( ) Tayaaja ( ) . The deposit ( ) 130 kilometers due east of the continental divide and approximately 290 kilometers east-southeast of Lima (Figure 1). Relief in the immediate vicinity of the mine, which lies or the west side of the Mantaro river, is in excess of 2,000 meters, and the elevation varies from a low of 2,000 meters above sea level on the Mantaro River to a high of 4,386 meters at point T-27 (Figure 2). Although the Cobriza deposit was first reported by the Italian Geographer Antonio Raimondi in 1866, only three reports have been published on the deposit, which began production in 1966 (Duefias, 1908; Fernandez Concha and Garcia y Garcia, 1961; Petersen. 1965). Many private reports have, however, been written by geologists employed by the Cerro de Pasco Corporation. These reports and the author's observations, while employed as the Cobriza Division Mine Geologists form the basis of the present paper, which describes the relations between-the ore controls in the Cobriza mine and the regional and local structure.

Jan 1, 1971

The article, as written, represents a short account of the treatment of the base bullion from the Broken Hill ores, as carried on at Port Pirie, for the recovery of lead, silver, and gold, and for the treatment of by-products. Appended is a short description of the chief facilities of plant which have been adopted to overcome the main difficulties in the refining of lead the Howard press and stirrer. The article is within the limit prescribed by the regulation for the prize offered by the Australasian Institute of Mining Engineers, comprising 30 pages, containing an average of about 200 words per page, exclusive of analyses, photographs, and sketches.The writer desires to thank those to whom he is indebted for their- kindness in affording him every facility possible to obtain the information which he required for the success of such a paper-viz., Messrs. Robertson, Leavens, and Gronow, of the Broken Hill Propritary Co. Limited, at Port Pirie, and Mr. Crowther, of the Adelaide School of Mines, to whom he is indebted for photographs. The difficulty of obtaining fair samples of gold drosses, and the inability to obtain particulars of fuel consumptions, prevents the paper from being as complete as one would wish. The limited length precludes detail, except in more important parts.

Jan 1, 1907

By J. N. Hilton, D. Moffett, E. Barnes

"A recent pilot-plant program carried out at Rio Algom's Quirke uranium mine at Elliot Lake, Ontario is described. The goal of the research was the production of tailings basin effluents which were low in total radium-226. The process tested involved precipitation of radium with barium chloride and sedimentation in plastic-lined settling ponds. Adjustment of the tailings basin overflow from its normal value of pH 9.5 by addition of sulphuric acid to about pH 7.5 was found to give approximately a five-fold improvement in total radium-226 removal. A five-month demonstration test resulted in an effluent with a mean total radium-226 activity of44 pCi/L after 2.5 days settling time and 29 pCi/L after 5 days. The results from the demonstration program are used to propose a schedule of achievable total radium-226 activities where precipitation and sedimentation are employed. The maximum suggested values for 5 days nominal settling time are: 30 pCi/L in an annual mean, 45 pCi/L in a monthly mean. 60pCiIL in a weekly mean and 80 pCi/L in any single grab sample.IntroductionRadium-226 has been removed from effluents at the Elliot Lake uranium mines since the introduction of the first barium chloride treatment system in 1965. Current practice, which has changed little over the years, consists of radium-barium sulphate precipitation by the addition of a low do se of barium chloride to the clear overflow from the tailings basin(l·2l. Provision is made for the precipitate to settle in large natural or constructed ponds and lagoons. The residence time in these ponds, which depends on the site, ranges from 3 to 35 days, with varying degrees of efficiency being achieved."

Jan 1, 1981

By Wightman D, Hoyle M. W H, Peters W. S

The Radio Hill nickel-copper deposit is located 30 km south of Karratha. It is a new discovery in an area where similar mineralization had been previously discovered at Mt. Scholl and Ruth Well. Radio Hill is the first massive Ni-Cu sulphide deposit of economic significance to have been located in the Western Pilbara.Preliminary studies indicate that the sulphide mineralization occurs within gabbros, pyroxenites and peridotites of a basic igneous cumulate layered sequence. Primary sulphides have been subsequently remobilized and concentrated as stringer and massive mineralization. This is tentatively attributed to the intrusion of a further gabbroic body.The deposit appears to be of the gabbroic association type with a Ni:Cu ratio varying from 1:4 in the outer parts of the mineralized envelope to 1:0.9 towards the central zones. In drill core observations, chalcopyrite surrounding pyrrhotite was noted in many instances. Drilling has so far delineated a body developed over a strike length of 600 m and a horizontal width of up to 25 m. The mineralization plunges 20° to the southwest with a southerly dip varying from 75° in the west to about 20° - 30° in the east.The deposit is a leaf-shaped ore zone, plunging southwest from a vertical depth of 17 m in the north to 300 m in the south. The massive sulphides occur as lensoid masses within this zone. A geological resource of up to 2.5 million tonnes at 1.5 per cent Ni and l.4 per cent Cu is indicated.The predominant sulphides are pyrrhotite, chalcopyrite and pentlandite, with significant cobalt, platinum group metals and gold. Tellurides of Pd, Bi and Pb were detected by scanning electron microprobe within the pyrrhotite and other trace metals include Zn and native tin. Massive magnetite is sometimes associated with the massive pyrrhotite intersections.A test on one composite massive sulphide sample showed that pyrrhotite is present mainly as the non-magnetic hexagonal variety and only 10 per cent is present as magnetic monoclinic pyrrhotite.The deposit has no surface expression and its identification was based mainly Oil drilling targets generated by geophysical methods. No secondary minerals have been observed in association with the primary sulphides, even though the deposit is only 17 m below surface in the northern part.

Jan 1, 1987

By John C. Taylor

"The non-ferrous pyrometallurgical industry has been under extreme pressure since 1980 and significant changes are taking place, principally in the copper, nickel and lead industries. This paper reviews some of these changes, particularly with respect to smelter capacity, major technical trends, and the industry's response to increased energy costs and environmental constraints.The Canadian metal mineral production for 1985 has been estimated at a value of over $8 billion, of which half is derived from copper, nickel, lead and zinc production. It is in our national interest that the Canadian industry remain competitive in the world market and continue its traditional contribution to the Canadian economy. IntroductionPyrometallurgy by definition requires energy, usually in the form of fuel, and produces process gas streams which can no longer be discharged directly to atmosphere in most countries. While the industry has been under varying degrees of pressure over the past fifteen years, it is just since the early 1980s that major changes have taken place, due, to a large extent, to an oversupply on the primary metal markets and depressed prices. These factors, combined with a surge in the price of oil, have resulted in some trends developing which must be recognized by those in the industry who plan to be in operation and competitive in the next decade.Although the value of Canada's mineral production, in terms of constant dollars, has decreased by more than 35% over the period from 1980 to 1985, the bulk of this production is exported and the industry still makes a significant contribution to the Canadian economy."

Jan 1, 1988

By Mario Mauro

Tuttle Creek Dam was constructed by the U.S. Army Corps of Engineers in the 1950?s on the Big Blue River in north-east Kansas. Since the dam is located in a seismic area, the safety of the dam was re-evaluated under the national U.S. Army Corps of Engineers Dam Safety and Assurance Program. After a series of studies and analyses performed by the Kansas City District of the U.S. Army Corps of Engineers, in 2003 the Department of the Army authorized the implementation of the plan ?Stabilize Foundation Soil without Drawdown Alternative?, during a 7-10 year construction period. As part of this plan, in 2006 Treviicos South carried out a large scale jet grouting and deep mixing test program downstream the dam. The test program included the installation of twenty-seven double and triple-fluid jet grout columns and twenty-seven jet-assisted deep mix columns. The jet grout columns were constructed at different levels of specific energy and cement content. The deep mix columns ranged in diameter between 3 ft and 6 ft. During column placement, the drilling and grouting parameters, pore pressures, and soil movements were instrumented in real-time. The downstream test area was enclosed by a cement-bentonite wall extended to bedrock, which allowed a 35-ft deep open excavation around the 45-ft deep columns. The exposed jet grout columns measured up to 15 ft in diameter, exceeding the anticipated target diameter. In addition to coring, some of the jet grout and soil mix test columns were saw-cut along the group axis, providing useful information on the internal column structure.

Jan 1, 2008

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962