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By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO'AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor' and Kay and alor' determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.' , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By Tony B. Szwilski, K. Unrug

INTRODUCTION Since the introduction of longwall coal mining systems, reliable predictions of roof support requirements at the face and the roof caveability in the gob area have been major contributors to the success of the longwall face by means of safety and face productivity. That is, the successful operation of a longwall is well-served by good regular caving of the gob. In recent times, with the advent of increased coal face mechanization and capital investment, the evaluation of the feasibility of longwall mining has become essential. In the United States, where a face unit for a face length of about 150 metres may cost around $6 million, a quantitative system that would assist in selecting the best equipment for the coal would prove extremely beneficial. There have been many such varied investigations in the past few years. A vast -amount of work has been invested principally by West Germany [3, 7, 8, 91 , Poland [I, 101 , United Kingdom [4, 5, lo], France [4], and South Africa [4]. It is the object of this paper to review this previous research work and give an outline that may be used as guidelines for long- wall evaluation. Essentially, for the initial design phase for a longwall system, account must be taken of the geometry of the coal panel, its position relative to the surface (depth), direction of the coal cleat system, faults and in-situ stresses and other neighboring workings in the same coal seam and other seams both above and below. The advance of the coal panel disturbs the stress field and in doing so creates an abutment zone around the face. At this stage the condition of homogeneity of the surrounding rock mass does not apply. The magnitude of the rock strata pressure may exceed the ultimate strength of the rocks and create zones of clastic, plastic and elastic material, the limits of which are difficult to determine. The collapse of the gob and resulting expansion of the displaced waste roof rock, create a statically undefined support complicating an already unclear rock structure. For example, it is often a point of debate whether, indeed, the vertical strata pressure develops to regain the original magnitude of virgin stress. Under these post-failure circumstances an analytical approach based on simplified and idealized assumptions can only be considered a very general approximation. Theoretical concepts, however, may be adequately supplemented by empirical methods that are based on numerous underground observations and surveys [3, 4, 7, 8]. These methods employ the use of rock indices that very handily correspond to the competence of the roof rock mass. Scale model work [3, 41 , using equivalent materials representing the surrounding rock mass within the coal seam zone, have given valuable qualitative and sometimes quantitative data in addressing the behaviour of the rock mass around longwall panels. To characterize the state of art of caveability predictioqthe principal concepts will be reviewed with special emphasis placed on practicality for the planning of longwall operation. It has been the general observation of the authors that many of the literature surveys published in English often neglect reference to other international mining literature. It is with this point in mind that an overall review has been written including mining concepts identified with the principal coal mining countries. THEORETICAL CONCEPTS Arching Theory For the development of this theory, assumption has been made that an extracted height, h, in a coal seam results in an extracted panel of width, w . Also, the coal seam is horizontal and the rock strata of both the roof and floor are homogeneous. The primary (virgin) stress distribution will change in the roof as well as the floor. As a result of lack of support caused by the excavation (in the gob area) an additional load is developed due to the redistribution of the load around the sides of the panel, referred to as the abutment, R, where: [ ]

Jan 1, 1982

By R. M. S. B. Horta, W. T. Roberts, D. V. Wilson

Evaluation of results obtained by the Harris method for inverse pole figures is discussed. Two existing analyses and a new approach are compared. In the most frequently used analysis, different reflections are accorded equal weight. A second method involves area-weighting of reflections, mainly to take account of nonuniformity of Pole distribution. In the new method, reflections are weighted according to their multiplicity factors. Intensity ratios obtained from a sample of steel sheet by the three methods are compared. INVERSE pole figures offer a convenient method of depicting the proportions of material with various orientations referred to a unique specimen axis. The technique was first applied to fiber textures, but it is now frequently used as a description of texture in sheet metal, the unique axis in this case usually being the sheet normal. The Harris method' for the determination of inverse pole figures has the great merit of simplicity. It suffers certain intrinsic limitations, but provided that these are borne in mind, the results allow useful conclusions to be drawn regarding the effects of texture components on certain mechanical properties. Much thought has been given to alternative methods of texture description, aimed at eliminating the ambiguity in the simpler methods.2"6 Refinements in the method of description are obtained at the price of increasing complexity, and it seems clear that a simple method, such as that of Harris, will continue to find application. The original derivation by Harris1 has been corrected by Morris7 and later by Mueller, Chernock, and Beck.2 Since the latter reference is more accessible, it is referred to more frequently than the work of Morris. Most users of the inverse pole figure method present their results on the basis of the treatment by Mueller et al., and it is the purpose of the present communication to comment on this treatment and to suggest a simple modification to the method of presentation which enhances the meaningfulness of the results. It will be convenient first to summarize the Mueller analysis as follows: The intensity Ihkl of a hkl reflection from a textured specimen is: Ihkl=CI0AL\Fhkl\2NhklPhkl [1] where C is a constant for a given sample I, is the intensity of the incident beam A is an absorption factor. With usual diffrac-tometer geometry and a flat specimen, A is inversely proportional to the density of the specimen. L is the Lorenz polarization factor Fhkl is the structure factor for the hkl reflection Nhkl is the multiplicity factor phkl is the fraction of crystals in the polycrystal-line aggregate with any particular (nkl) plane parallel to the surface. The corresponding equation for a specimen with randomly oriented grains is lR,hkl=CRl°ARL\fnkl\2Nnklk [2] the subscripts R indicating the factors that are different for the random sample, which will, in general, have a density different from that of the textured one. The intensity ratio is hkl , c A Phkl [3] IR,hkl CR AR PR The constants are eliminated by summing over all the measured reflections ^iRMi °R AR PR ljPkkl and from Eqs. [3] and [4] T IR,hkl The only unknown in Eq. [5] is Yj phkl and before this can be evaluated, it is necessary to adopt some form of normalizing procedure. Mueller et al. assume that when a large number, n, of reflections is used, the average value of p as defined by Eq. [6] below will be unity ? = £j**l3l [6] and the final result of their analysis follows: hkl Pkkl = i I&Jf~ [7] ±y* Ihkl ^ in,hki The normalizing procedure used by Mueller et al. involves an unrealistic assumption since it gives equal weight to each of the hkl reflections. Other normalizing procedures can now be examined with a view to selecting a more appropriate one. For an infinite number of reflections, the function p can be averaged over a continuous range of orientations covering the complete solid angle 4p by the integral relation: p =1 jp(a)dQ = l [8] This is the only exact procedure, but in practice a

Jan 1, 1970

By R. S. Wagner, W. G. Pfann

METHODS that have been used to measure stress relaxation in metals and plastics have been reviewed recently by G. R. Gohn and A. FOX.' The ideal stress relaxation test comprises placing a sample under a constant strain (usually considered

Jan 1, 1962

By R. M. Treco

The effect of small additions of oxygen on the hardness, density, and lattice parameters of high purity zirconium has been investigated. Precision parameter values and density of oxygen-free zirconium are given as: a,, - 3.2258 kX units, C = 5.1373 kX units, O23 = 6.507 g per cc. THE effect of oxygen on the hexagonal-phase lattice constants of pure zirconium is of interest for several reasons. The extensive hardening effect of oxygen noted by previous investigators' must be due in part to the lattice distortion accompanying its introduction and possibly to the preferred position of the oxygen atoms. De Boer and Fast' have shown that oxygen is taken into solid solution in large amounts, appearing to occupy an interstitial position. These authors also found that expansion of the lattice was not uniform since the a axis attained a constant value after the addition of 10 atomic pct while the c axis continued to expand. It was thought in the present work that this expansion of the zirconium lattice with increasing amounts of oxygen

Jan 1, 1954

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By J. E. Spruiell, F. H. Patterson, B. F. Shuler

The microstructures and textures developed by the working of high-purzly thermochemically deposited tungstem sheet have been inuesligated. Greater than 60 pct reduction was required to deslroy the columnar grain structure which existed in the as-deposited sheet. With increasing reductions the texture gradu-ally charged from the initial as-deposited orientation with (100) parallel to the sheet normal to a (100}(011) ideal ovienlation with some spread about the rolling direction. This texture was retained after recrystalli-zation a1 2000°C. THE processes for depositing tungsten by hydrogen reduction of tungsten hexafluoride have been under development for the past several years.1,2 The nature of the deposition process is such that the as-deposited material contains a highly oriented columnar grain structure perpendicular to the deposition substrate. This well-defined columnar structure may be useful in certain applications293 but a wrought or equiaxed structure may be desired for some components such as tubing. Knowledge of the effects of working ther-mochemically deposited (TCD) tungsten is therefore necessary in order to establish the feasibility of obtaining worked and recrystallized microstructures and textures. The details of a recently developed technique for thermochemically depositing flat, uniformly thick tungsten sheet are presented with emphasis on the effects of deformation by rolling on the microstructure and texture. Although no work has been previously reported on the rolling and the annealing textures of TCD tungsten, there have been some determinations of textures for cold-rolled tungsten foil prepared from powder-metal -lurgy billets.4-8 The general description is that of a predominantly lurgy{100}(011) texture, with some spread about the rolling direction as an axis. pugh5 reports data both for cold-rolled and for annealed foil having about 96 pct initial cold work. He observed no change in texture, except for a decrease in the spread, for annealing treatments of 30 min at temperatures up to 1800°C. On annealing at 1900°C, both the low-temperature components plus new components which were described alternately as {001}(320) plus {001)(230) or as {100}(011) ± 12 deg about the sheet normal were observed. Above 1900°C, the new orientation existed alone, and it was stable up to 2500°C, the highest temperature that Pugh investigated. THERMOCHEMICAL DEPOSITION OF TUNGSTEN SHEET High-purity tungsten sheet was reproducibly deposited on the inner walls of a molybdenum mandrel by the thermochemical reaction WFs(g) + 3H2(g) - W(s) + 6HF(g). The mandrel was heated by a five-zone tube furnace which afforded a controllable fixed-temperature profile. Sheets measuring 1+ by 12 in. have been deposited with uniform thicknesses of up to 0.145 m. As shown schematically in Fig. 1, the purified reaction gases were metered into a mixing chamber at a Hz-to-WF6 ratio of 15 and preheated to 350°C. The flow rate of the WF6 was 300 cu cm per min at stp. These gases were directed through a conical injector into the deposition chamber. Inside this chamber hydrogen reduction of the WF6 to pure tungsten metal occurred on the hot walls of the molybdenum mandrel at a total pressure of 5 Torr. Typical temperatures for the five zones in the chamber were, respectively, 565", 540", 550°, 570°, and 590°C. The hydrogen fluorlde generated from the reaction, the excess hydrogen, and some un-reacted WF6 were pumped on through the scavenger

Jan 1, 1968

By WILLIAM SLOAN

B RITISH COLUMBIA in its mining activities is going ahead by leaps and bounds both in development and production. Mineral production for 1925 was $61,492,242 in value as compared to $48,704,- 604 in 1924, or an increase of about 26.2 per cent. This is a new record. It is the first time in the history of mining in British Columbia that we have gone over the fifty million mark. But we have got in the habit of making new records. The year 1924, with its mineral production of almost forty-nine million was a new record. And I am confident that when the mining history of 1926 is written it will be found that we have established yet another new record and that we can report another 25 per cent increase over 1925. What is the explanation? It is not only that the world is settling down, and settling up, after the war. It is not only that in the rebuilding, the refashioning in which all nations are busily engaged, the metals that come from our mines are needed. More than anything else, at least as far as we are concerned, it is because British Columbia has the resources and the fact that the province has been fortunate in recent years in finding men with the enterprise and the vision required to push ahead the labor of their development. From the ranks of our own people in Canada we have prospectors who have faith, energy and requisite knowledge. They are combing our hills season after season and they are of the type of manhood that does not know the meaning of the word quit. More and more these men are learning the importance of the guidance furnished by geological reports, and to an ever increasing extent such reports, thanks to the valuable work of the Canadian Geological Survey, covering areas little known to man, are made available to them-but it is recognized that in the opening up of our Province, containing within itself 372,000 square miles, it is essential that we should have the cooperation of our cousins on this side of the line as well as of our fellow citizens of the Dominion and of the Mother Country.

Jan 1, 1926

By CHARLES M. A. STINE

THE value of chemical research has been so thor¬oughly demonstrated in the last few decades that the general public has become "research-conscious" to an extent which allows the advertising agent and publicity man to make use of research as a selling point in his advertising campaigns. We thus see the advertisements of concerns in the most varied industries stressing the research which is back of their products. The reason for this "research-consciousness" of the general public. is primarily that the products of research have increasingly engaged public attention and have. revolutionized our daily life. When we. reverse the flight of .time and imagine ourselves-in the century previous to our own, we find that we are .without the automobile, the radio, the improved telephone and electric light, refrigerated transportation, the airplane, X-rays, and many other things now taken for granted. A generation ago we find gloomy prophets foretelling the certain over-population .of the world within a few decades and an insufficiency of food due to lack of the fixed nitrogen which is now so plentifully ours.

Jan 1, 1930

By J. Rogers, K. L. Sutherland

THE relationships between collector and mineral, activator and mineral, and activator, collector and mineral will be considered herein. We propose to criticize current theories of flotation but we will not repeat the many pertinent arguments presented by Wark and Cox28 in 1937 in which the "chemical" or more strictly the "solubility" theory proposed by Taggart and co-workers22 is shown to be untenable. Recently Taggart, Arbiter and Kellogg24 have studied the long-chain aliphatic amines as collectors and have attempted to resuscitate the solubility theory for these particular collectors. Dean and Ambrose3 have felt that "we stumble over words" when we distinguish different mechanisms of adsorption. Our view is that nothing is more stultifying to the development of a science than attempts to force widely different phenomena into one classification. This oversimplification leads immediately to difficulties in the interpretation of results. EXPERIMENTAL PROCEDURE The response of minerals to activator and collector was determined by "captive-bubble" tests. The methods of preparation of specimens26 and of testing18 have been previously described. Results from captive-bubble tests were confirmed by flotation tests in glass-stoppered cylinders.25 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible by a cross and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, the experimental results being indicated on the figures by a square. The curves show the limits of composition of solution in which flotation in a cell would be possible. Many factors other than those considered in these tests determine recovery or grade of a given mineral in practice.

Jan 1, 1947

By Harold Margolin, W. R. Hibbard, R. W. Fenn, H. P. Moore

Deformation lines, also called etch markings or strain markings, are non-effaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries. Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrett2 to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation requireti for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted defor- mation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson6 observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brickg noted that deformation lines in 70-30 brass apparently associated with I I I I ) planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards" reported that in Copper cold rolled less than about 50 Pet few strain markings were apparent but for higher reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass below 20 pet reduction and added that 4

Jan 1, 1949

By H. P. Moore, R. W. Fenn, Harold Margolin, W. R. Hibbard

Deformation lines, also called etch markings or strain markings, are non-effaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries. Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrett2 to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation requireti for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted defor- mation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson6 observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brickg noted that deformation lines in 70-30 brass apparently associated with I I I I ) planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards" reported that in Copper cold rolled less than about 50 Pet few strain markings were apparent but for higher reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass below 20 pet reduction and added that 4

Jan 1, 1949

By J. W. Schroeder

SEAMLESS pipe, the product produced from piercing a solid round billet of steel by the Mannesmann process, was first produced in the latter half of the 19th century, the Mannesmann machine having been patented in 1885. The products of other processes also have been termed seamless pipe; for example, the cylindrical section produced by "cupping," which consists of forming a cup from a flat plate or disk and further elongating the cup into a tube by passing it through a set of reducing dies. The purpose of this paper is to discuss some of the more important metallurgical factors and their relationship to the economical production of seamless pipe produced by the Mannesmann piercing process. The first seamless tube plant in America was established at Shelby, Ohio, in 1891, and was employed in the manufacture of bicycle tubing. For a number of years the bicycle industry was the only user of seamless tubing, and this tubing was produced by hot-rolling pierced billets imported from Europe and finishing on the cold drawbench. At the turn of the century, the automotive industry was responsible for an increase in the demand for seamless tubing. The growth of this industry was the dominant factor leading to the phenomenal growth of the petroleum industry, which in turn created a tremendous demand for seamless pipe. In addition; the old lapweld iron boiler tubes for stationary and locomotive boilers were replaced gradually by seamless tubes. Since 1929, the production of seamless steel pipe and tubes has increased over loo pct. In 1929, 1,459,9031 net tons of seamless pipe was produced, including both hot-finished and cold-drawn material, as compared with 3,087,3122 net [ ] tons in 1948. Table I gives the distribution of seamless pipe by classes for 1948. METALLURGICAL PROBLEMS From a metallurgical standpoint, the production of seamless pipe has presented many problems. Practically every type of steel, carbon and alloy, with the exception of the superalloys developed during World War II, has been pierced and rolled successfully into tubing. This includes bessemer, open hearth, by the stationary and duplex processes, and electric steels. The range of sizes produced is no less staggering to the imagination, when it is considered that the hypodermic needle, which is 0.016 in. diam with a wall thickness of 0.004 in., and pipe for gas or oil transmission lines, with a 26 in. OD, are both seamless tubes. Between these extremes, the range of diameters and wall thicknesses meets most present-day demands for seam-

Jan 1, 1951

Granduc lies near the Alaskan border in British Columbia, about 600 miles (960 km) north of Vancouver. Prospecting in the area must take place in the short summer months of fog and rain because the winter is bitter cold, with snowfall up to 960 inches (24.4 m) accompanied by avalanches. Despite these difficulties, the mineral ized area was discovered in the 1920's. By 1956, Newmont Mining Corporation had developed mineable ore reserves estimated at 32,500,000 tons of 1.93% copper. Newmont and ASARCO, in a joint venture, then began development of the ore body, which was partially covered by glaciers. It was apparent a concentrator could not be built at the mine site where overland access was impossible due to the weather conditions and the terrain. Years of engineering studies of all possible access routes finally dictated the driving of an 11 mi long (17.6 km) tunnel passing under three glaciers and three mountain ranges to the nearest feasible concentrator site at Tide Lake. Even then, a mountain road subject to an average snowfall of 800 in. (20. 3 m) had to be built 32 mi (51 krn) from the concentrator through Alaska to Stewart, British Columbia, the nearest port. At Stewart, which is located at the head of a fjord 120 mi (192 krn) from the Pacific Odean, a fully equipped marine terminal was built. The tunnel, the lifeline between mine and mill, was to be driven from both ends; however, in 1965, an avalanche occurred at the Leduc portal, killing 26 crew members and wrecking much of the camp. The tunnel was then driven from one heading adjacent to the concentrator site at Tide Lake, a distance of 53,744 ft (16,381 m) to a point under the ore body. The remote location, type of terrain, and bad weather made supply of crews, equipment, and construction materials difficult; but in spite of these extremely adverse conditions, the tunnel crews set many world records. Mineralization throughout the ore zone is generally uniform in grade and composition and is primarily chalcopyrite and pyrrhotite associated with pyrite. Mining is mainly by sublevel caving. After blasting, rubber-tired load-and-haul equipment moves from level to level by means of an internal connecting ramp system on a 15% slope. At the gathering haulage level, 15-ton bottom-dump cars deliver the ore to a 600-ton pocket equipped with a Hudson "Rock-Flo" dump. The bottom of the ore pocket forms the feed chute to the primary

Jan 1, 1978

By McHenry Mosier

MeRcuRy is one of the strategic metals of which the supply has been raised from critical uncertainty to more than enough for essential demands. Work by the Bureau of Mines has contributed substantially to increased production of mercury in the United States and to consequent accumulation of Government stocks. Other contributing factors have been higher prices for mercury and Government loans to operators. The Bureau has undertaken 13 exploration projects, 10 of which have been completed. This work has comprised 28,376 ft. of several types of drilling and 23,798 lin. ft. of surface trenching, and has indicated commercial ore containing 34,800 flasks of mercury and marginal ore containing 26,200 flasks, a total of 61,000 flasks; equivalent, respectively, to domestic production for 8 months, 6 months, and 14 months. As Government stocks are now adequate, domestic production (currently at the rate of 50,000 flasks per year) is gradually being curtailed through Government control of labor and operating supplies. Introduction Mercury was one of the seven metals designated as strategic by the Army and Navy Munitions Board in 1939, when Congress appropriated funds for the investigation of domestic sources of supply of war minerals. The Bureau of Mines immediately started a limited search for strategic minerals, but the first mercury project was not begun until December 1940. The U. S. Geological Survey assisted in the search for cinnabar by contributing information on domestic mercury deposits, preparing maps, and making geological studies of exploration projects. The present high rate of production of mercury in the United States was encouraged by the increase in price to $196 per flask at New York (Fig. I) and Government loans to operators for mine development and plant construction. The Bureau of Mines has issued, for restricted distribution subject to wartime controls, 13 War Minerals Reports on individual mercury deposits (listed in appendix A). In March 1942 it also published a Progress Report of the Metallurgical Division, R. I. 3627, Cinnabar-reduction Plants of the Southwestern Arkansas Quicksilver District. Uses of Mercury Mercury and its compounds have more than 3000 uses. Its principal use is as a catalyst in the manufacture of gases for chemical warfare; the next largest is in pharmaceuticals. Mercury is essential also for: (I) certain electrical apparatus, (2) industrial control instruments at many war plants, (3) munitions, including blasting caps, (4) insecticides in agriculture, (5) antifouling paint for ship bottoms, (6) dental preparations, (7) general laboratory use, and (8) amalgamation of free-milling gold ores.

Jan 1, 1949

By McHenry Mosier

MeRcuRy is one of the strategic metals of which the supply has been raised from critical uncertainty to more than enough for essential demands. Work by the Bureau of Mines has contributed substantially to increased production of mercury in the United States and to consequent accumulation of Government stocks. Other contributing factors have been higher prices for mercury and Government loans to operators. The Bureau has undertaken 13 exploration projects, 10 of which have been completed. This work has comprised 28,376 ft. of several types of drilling and 23,798 lin. ft. of surface trenching, and has indicated commercial ore containing 34,800 flasks of mercury and marginal ore containing 26,200 flasks, a total of 61,000 flasks; equivalent, respectively, to domestic production for 8 months, 6 months, and 14 months. As Government stocks are now adequate, domestic production (currently at the rate of 50,000 flasks per year) is gradually being curtailed through Government control of labor and operating supplies. Introduction Mercury was one of the seven metals designated as strategic by the Army and Navy Munitions Board in 1939, when Congress appropriated funds for the investigation of domestic sources of supply of war minerals. The Bureau of Mines immediately started a limited search for strategic minerals, but the first mercury project was not begun until December 1940. The U. S. Geological Survey assisted in the search for cinnabar by contributing information on domestic mercury deposits, preparing maps, and making geological studies of exploration projects. The present high rate of production of mercury in the United States was encouraged by the increase in price to $196 per flask at New York (Fig. I) and Government loans to operators for mine development and plant construction. The Bureau of Mines has issued, for restricted distribution subject to wartime controls, 13 War Minerals Reports on individual mercury deposits (listed in appendix A). In March 1942 it also published a Progress Report of the Metallurgical Division, R. I. 3627, Cinnabar-reduction Plants of the Southwestern Arkansas Quicksilver District. Uses of Mercury Mercury and its compounds have more than 3000 uses. Its principal use is as a catalyst in the manufacture of gases for chemical warfare; the next largest is in pharmaceuticals. Mercury is essential also for: (I) certain electrical apparatus, (2) industrial control instruments at many war plants, (3) munitions, including blasting caps, (4) insecticides in agriculture, (5) antifouling paint for ship bottoms, (6) dental preparations, (7) general laboratory use, and (8) amalgamation of free-milling gold ores.

Jan 1, 1949

By R. A. Sharma, F. D. Richardson

Manganese oxide acitivities and sulfide capacities have been measured at 1650°C in mixtures of MnO + A1203 and MnO + SiO2 - Al2O3. Sulfide capacities have also been measured at 165O0C for melts of MnO + SiO2, MgO + SiO2, MgO + SiO2 + Al2O3, MgO + MnO + SiO2, and SiO2 + Al2O3 and for crystalline CaO. The activity coefficients of the sulfides of manganese and magnesium have been derived where possible. It looks as though the activity coefficients of sulfides are greatest at compositions where the free energies of formation of the silicate mixtures have their maximum negative values. The amphoteric nature of alumina is reflected in the results for the binaries and ternaries in which it is present with silica. The limiting solubility of CaS in CaO at 1650°C is 6.3 x 10-4 mole fraction. THE activities of manganese oxide have been measured in a variety of silicate and aluminate melts by use of the equilibrium (MnO)slag = [Mn]pt .½O2 [l] and the experimental techniques described previously.' Sulfide capacities (CS = wt pct S (PO2/PS2)½) have also been determined in a series of melts, by use of an established method2 which exploits the equilibrium (O°) + ½S2 = (S") . ½O2 [2] If CS and the activity of a metal oxide are known in a melt, the activity coefficient of the metal sulfide can be calculated by use of the equilibrium constant K, for the pure phase reaction MO i ½S2 = MS + ½O2 [3] The activity coefficient of the sulfide is then given by the equation

Jan 1, 1965