Search Documents

By Clarence Zener

Contents Page General Principles................................................................. 551 Equilibrium Diagrams......................................................... 551 Nucleation................................................................... 553 Kinetics of Phase-boundary Propagation......................................... 553 Kinetics of Growth of New Phase............................................... 556 Spheroidization............................................................... 560 Pure Iron-carbon System........................................................... 561 Formation of Pearlite.......................................................... 561 Interlamellar Spacing........................................................ 562 Pearlite C-curve............................................................. 563 Bainite Formation............................................................. 565 Formation of Martensite....................................................... 570 Loss of Tetragonality of Martensite.............................................. 570 Effect of Alloys upon Decomposition of Austenite..................................... 572 Pearlite...................................................................... 572 Bainite and Martensite......................................................... 574 Time-temperature-transformation Curves............................................. 576 Appendix A............................................................. ......... 579 Appendix B....................................................................... 580 Appendix C....................................................................... 580 The present investigation started in an attempt to understand certain details of the decomposition of austenite, and of the effect of alloying elements thereon. As the investigation proceeded it became apparent that not only these details, but all the general features of austenite decomposition, could be understood in terms of fundamental physical principles. Since the direct applicability of these physical principles has not been previously recognized, it was decided to incorporate the original results of the investigation into a review of the general subject of the kinetics of austenite decomposition. This review constitutes the present article. An extended summary of the results is given on pages 576 to 579. This article, which deals with the kinetics of phase transformations, may appropriately be considered as a sequel to two recent articles1,2 from this laboratory on the equilibrium relations in medium alloy steels.

Jan 1, 1947

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947

By Zay Jeffries

This paper will include a brief discussion of Prof. Howe's paper on The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite.l The general subject of grain refining in steel and iron will also be treated. The conclusions reached are stated in the following hypotheses which are discussed more in detail below. 1. The ferrite grain size in pure iron, the ferrite and pearlite grain size in hypoeutectoid steel, the pearlite grain size in eutectoid steel and the cementite and pearlite grain size of hypereutectoid steel are not inherited from the grain size of the mother austenite. 2. The only structural feature that is generally inherited from the austenite of hypo- and hypereutectoid steels on cooling through their transformation ranges is the position of the excess ferrite or cementite at the austenite grain boundaries, sometimes causing complete and sometimes incomplete networks which outline the old austenite grain boundaries. Rapid cooling through the transformation range will cause the non-inheritance of this structural (network) feature. 3. The austenite grain boundaries themselves are nearly always effaced in all steels and also in pure iron during the At transformations. 4. The grain-size refining of steel and iron is brought about by the combined effect of non-inheritance of the transformation products on either heating or cooling, i.e., the austenite transformation products do cst inherit their grain size from the austenite on cooling through the transformation range nor does austenite inherit its grain size from the products which form austenite on heating. 5. In general, in both iron and carbon steel the larger the austenite grain size, the larger will be the grain size of the transformation products on cooling. This, of course, assumes all other conditions constant except the austenite grain size. An exception is found to this general rule in very pure iron such as electrolytic iron. In this instance small austenite grains may form very large ferrite grains on cooling through Arg.

Jan 1, 1918

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947

By C. H. Cheng, C. E. Birchenall

The fundamental problem in the thermodynamics of solid solutions is the determinatiorl or calculation of the activities of the components as a function of temperature and composition. Since the theory of metals is not suficiently developed to allow a priori calculation of these quantities, they must be obtained from experiment. C. Wagner1 has reviewed the literature of this subject for the period before 1940. Although several important and extensive studies have been made in the meantime, the number of systems to which any sort of quantitative information can be assigned is vanish-ingly small. These data have become of great potential importance in studies of the structure of solid solutions2 and intermetallic compounds, the nature of the diffusion process,3,4 and perhaps even the mechanism of mechanical deformation.5 For these reasons, it. seems very worthwhile to extend the experimental data in this field. Although there is little use in duplicating Wagner's review, attention should be directed to the most recently reported investigations. A brief enumeration of the methods of measurement previously employed also should be valuable. The most direct method is the determination of the partial pressure of the components in the vapor phase in equilibrium with the solution. Both equilibrium and kinetic methods have been tried in metal systems, but almost exclusively on liquid phases. Only in the ease of carbon in iron alloys and in the copper-zinc system have extensive measure- ments been made which include solid phases. When one of the components is an element, such as nitrogen or carbon, which forms compounds which are very volatile and stable at normal temperatures and pressures (CH4, Co2, CO NH3), it is frequently possible to equilibrate mixtures containing these (such as CH4-H2, CO2-CO, NH3-H2) independently with the elernents (C, X) and with the metal (Fe, Ni, etc.). Such measurernents have been made for carbon in iron, iron-silicon, and iron-manganese alloys by Smith6 and in iron and iron-nickel alloys by Toensing.7 Differences between carbon activity values at the same temperature and carbon content when carboil is introduced from CH4-H2 rnixtures or CO-CO. mixtures indicate that the effects of hydrogen and oxygen in the system are not negligible, and one can only hope that the true value lies somewhere between these sets of results, probably nearer the CH4-H2 data since hydrogen is less soluble in iron than oxygen. This is essentially an equilibrium method, although flowing gas is employed. A kirletic method has been employed which consists of sweeping an inert gas (generally hydrogen) over the alloy at a series of rates, condensing the metal vapor out,, and analyzing it. The metal content can be extrapolated to zero flow rate (equilibrium). Wejnarth's8 work on Cd-Mg and Zn-Mg is a good example of this frequently used method. A variant of this consists of equilibrating a known volume of inert gas with the alloy, sweeping it out quickly, and analyzing for metal. In common with the above method, it has the disadvantage that the "inert" gas is generally somewhat soluble in the alloy. Moreover, the former continuously displaces the system from equilihrium and may give low values if solid diffusion is involved. The dew point method applied by Hargreaves9 to the alpha and beta brasses and by Schneider and Stolll0 to A1-Zn avoids the introduction of another component to the system, but is useful only in systems in which one component is much more volatile than the other. The alloy sealed in one end of an evacuated silica tube is heated to the desired temperature. The temperature of the other end is lowered until droplets of the volatile component condense. When the temperature is raised slightly, the droplets will evaporate. By careful adjustment of temperature, the range between evaporation and condensation can be narrowed appreciably. An independent determination of the vapor pressure of the . pure volatile component is necessary to give the partial pressure over the alloy. This is the method employed here to determine the vapor pressures of zinc and cadmium over their silver alloys up to 34 pct in cadmium and 76 pct in zinc. The former involves only the a solid solution, but the latter covers the a, ß, y, and e fields. In recent determinations, Herbenar, Siebert, and Duffenbarkl1 used the

Jan 1, 1950

By R. R. Harvey

Recent evidence has indicated that the films forming at crude oil-water interfaces are the result of naturally occurring su,rface-active components in the crude oil rather than oxidation products resulting from exposure of the oil to air. Since the presence of such films may strongly affect the displacement of oil from porous media, a knowledge of their composition and formatiorz is of fundamental importance. In this study, without the assumption of a specific mechanism, film formation is considered to involve the transfer of a weakly surface-active species in solution in the oil to the oil-water interface. The film gas law and the Gibbs adsorption equation may thus he applied to the system. The rigid films which form upon decrease of the oil-water interfacial area are considered a result of the very slow rate of re-solution of the film material into the oil. When the shrinkage of the interface is very rapid, the amount of film material leaving the interface is negligible, and the system may then be treated in the same manner as an insoluble film. The combination of these treatments leads to a new concept of the film factor in which it may he quantitatively related to the concentration of film-forming material at the interface. Suitable experiments can then yield the following information. 1. Original concentration of surface-active species in the oil. 2. The change of concentration with time. 3. Concentration of surface active species at the interface. 4. The change of this concentration with time. 5. Interfacial tension of the system at any time and its variation with time. 6. Equilibriunz concentrations for a given set of conditions. 7. Concentration requirements for solid film formation. 8. Molecular diameter of the adrorbed species. These calculations may be made solely from data taken from measurements on the original oil. While using the pendant drop method of interfacial tension measurement of crude oil-water systems, Bartell and Niederhauser' remarked on the thin, transparent, pliable, solid films or membranes which were often formed at the interface between crude oil and water. As a result of their observations of these films, Bar-tell and Niederhauser concluded: 1. The films are formed by material from the oil adsorbed at the interface rather than by a reaction at the interface. 2. The adsorption of the film-forming material is a rather slow process. 3. There are good indications that the process is reversible; i.e., the film constituents may re-dissolve into the oil. 4. The film will spontaneously spread over any new surface formed. 5. The process of adsorption at the interface is accompanied by a decrease in the interfacial tension of the system. Although they had proved that film formation was not due to a reaction at the interface, Bartell and Niederhauser were unable to demonstrate conclusively whether these film-forming constituents were present in the original reservoir oil or whether they were formed as oxidation products after exposure of the oil to air. Recent evidence seems to point to their presence in the original oil. Although the true nature of the film-forming constituents is still uncertain, these conditions would be fulfilled by the assumption of the presence of a slightly soluble surface-active component in the original oil. This component would migrate to a freshly formed interface because it would thereby lower the free energy of the system. The component at the surface constitutes an expanded monolayer which would become compressed, upon retraction of drop, due to the slow rate of re-solution of the film components into the bulk of the oil. It is possible, by involved extraction processes, to separate or at least concentrate this film-forming fraction. However, using the assumptions made above, the technique of monolayer film study may be applied to reveal much of the nature of the adsorbing material without resorting to an actual separation of the film-forming constituents.

By G. H. Matheson, J. M. W. Mackenzie

The flotation rate of coal has been studied using a continuous laboratory flotation cell and a multiple exposure photographic technique. The effects of particle size, reagent additions and cell turbulence on the flotation rate of coal have been investigated. The results have been analyzed in terms of current theories of particle bubble encounter and adhesion. The rupture forces which occur during particle bubble encounter have been shown to have an important effect on the flotation rate of coarse coal particles. The flotation of coal is a time dependent process, and in order to obtain a complete understanding of the operation it is necessary to determine the kinetics of the process. In coal flotation, the flotation rate and the associated values of cell productivity in terms of tons per kilowatt-hour and tons per cubic foot of cell volume are of greater importance than in most other mineral flotation operations. The reasons for this are associated with the low unit value of coal and the relatively high cost of coal flotation compared with other coal cleaning processes. An important aspect of coal flotation kinetics is the design of coal flotation cells. The cells used in many coal cleaning operations are often replicas of those used for the treatment of sulfide ores and are not necessarily suitable for the treatment of coal washing pulps, which usually contain a higher percentage of coarse and floatable material than the sulfide pulps for which the cells were designed. This disadvantage of many coal flotation cells has been recognized by Russian engineers who, by the addition of baffles to their subaeration coal flotation cells have increased the cell capacity by 100%. Investigation of the variables which influence flotation kinetics and cell productivity are, therefore, important to the coal industry where flotation is the only accepted method of cleaning the fine (-1/2mm) coal. The kinetics of the flotation process have been investigated in detail by Schumann10 who developed a continuous flotation cell which permitted the study of flotation under steady state conditions. This technique has been used by Gaudin et a1.,6 Brown and Smith and recently by Jowett and Savfi.7 The latter authors have developed a refined mathematical treatment for interpreting the results of continuous laboratory tests. Attempts have also been made to study flotation kinetics using conventional batch testing techniques. The experimental difficulties, however, and the problems of determining the order of the flotation rate process have made this technique of dubious value. A summary of the proposed rate equations for batch testing and the difficulties associated with this technique is given by Brown and Smith. 2 The experimental techniques described above are concerned with the rate of production of froth product. However, several authors, notably Sutherland, 11 Bogdanov1 and Philippoff, 9 have analyzed flotation

Jan 1, 1963

By Joseph Singewald

INTRODUCTION FOR a number of years Russia, India and Brazil have outranked .all other countries as producers of manganese ores. During the 5 years immediately preceding the European war, the average annual production of Russia was 844,000, of India 694,000 and of Brazil 200,000 long tons. Since the outbreak of the war there has been a considerable falling off in the Russian and Indian production, particularly in the former, whereas the production of Brazilian ores has been greatly increased, amounting in 1914 to over 250,000 tons and in 1915 to nearly 350,000, with conditions favorable for a still larger production in 1916. Manganese is one of the few industrially important metals that are not produced in the United States in quantity commensurate with our needs, so that we have been compelled to import annually about 300,000 tons, having a value of over $2,000,000, and these ores have been obtained from the three countries mentioned above. Their rank as contributors to our imports of manganese ores was India, Russia, Brazil; and in 1913, Brazil contributed only one-fifth. During the past 2 years Brazil has furnished rapidly increasing quantities to this country, and, with the falling off of imports from India and Russia, has become our principal foreign source. In 1914, Brazil furnished two-fifths of the imports and more than India or Russia, and in 1915 over nine-tenths. The manganese ores of Brazil are consequently of more than usual interest to us at this time.

Jan 10, 1916

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson's paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence' but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

By William R. Webster

This is a subject which our Institute has made peculiarly its own. In the first volume of its Transactions the analysis of steel received attention, and every subsequent volume has borne witness to the acuteness and industry of our members in the investigation of this subject. The keynote mas struck, in this as in so many other lines of progress, by A. L. Holley, in his paper on " Tests of Steel," read at the Easton meeting of October, 1873 (Trans., ii., 116)—an essay which may rank as a classic by reason of .its elegant form, logical force, and clear prevision of all the bearings of its theme, Taken together with the brief report of the discussion which followed it (in which Dr. Drown emphasized the effects of heat-treatment and mechanical handling, and Dr. Sterry Hunt the importance of minute variations in chemical composition, and of possible isomeric and allotropic conditions), it constitutes, after the lapse of twenty-five years, an admirable and adequate introduction to the long list of technical papers which have succeeded it. Three years later came the epoch-making papers of Dr. C. B. Dudley on the relation between the chemical composition and physical properties of steel rails, which, with the voluminous discussion they evoked, constitute a special volume, published by the Institute, and full of useful suggestions. If Dr. Dudley could be induced to resume this investigation, he would doubtless be able to solve many points still uncertain or disputed. But I cannot undertake to review the history of this subject, as represented in our Transactions—still less to restate all the contributions to it which have been made in books or in papers before other technical societies, since the initiative was taken by the Institute. My more modest purpose is to indi-

Jan 1, 1899

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By P. S. Miller, S. H. Ash

EXTENSIVE and diversified resources justify large populations and great industries. To carry on the business of commerce and meet the demands of large populations, the utilization of tunnels in some form for transportation purposes constitutes an important link in modern civilization. The driving of tunnels has been appropriated by the tunneling branch of the heavy-construction industry, and the progressive steps taken by modern tunnel builders were not even dreamed of 50 years ago. Great strides have been made toward more rapid progress in tunneling in the United States during the past 10 years. Tunneling consists of a definite cycle of operations developed from ideas that are crystallized and translated into action programs through various engineering phases that begin with the first preliminary survey and do not end until the job is completed. Once the line of the bore is established and a time set for the completion of the work, the face must advance according to estimates prepared before the work commences. This schedule must be followed in regular sequence from the moment the drills start against a new face of rock until they are ready again to drill the succeeding face, constituting a round.1 Mining is largely tunneling carried on under conditions often more inherently hazardous than actual tunnel construction, but for various reasons1 tunneling is more hazardous than mining in any branch of the mineral industry, On the other hand, obstacles are sometimes encountered in heavy-construction tunneling projects that when met in mining enterprises do not offer comparable tasks to avoid or overcome them. One of these is the existence of water under high pressures. In mining enterprises, various alternatives offer a solution in driving a tunnel, even to the extent of its discontinuance or the abandonment of the mine, but a "construction" tunnel usually must go forward because some important project depends largely if not entirely upon it. This paper describes an unusual method of driving a water-supply tunnel through rock carrying water under pressures and conditions that did not permit the use of ordinary tunneling methods. THE DELAWARE AQUEDUCT The new Delaware aqueduct is a Manhattan project of some magnitude; when completed, it will contain what probably will be, for some time to come, the longest tunnel in the world. Various features in its construction are currently described in the trade journals of the construction industry, and informative engineering details are given in the Delaware Water Supply News, published twice a month by the Board of Water Supply of the City of New York. Work was begun on this project on March 24, 1937. The tunnel will convey water from reservoirs at the headwaters of the Delaware River to the City of New York.

Jan 1, 1942

By E. R. Gilbert, D. E. Munson

Creep of copper under 75 to 1.50 kg per sq cm stresses at temperatures near the melting point was found to he a complex reaction controlled by three mechanisms acting in parallel. In order of appearance with decreasing temperature, the auerage activation energies, Qc , are 168, 79, and 24 kcal per mole. Stress dependence of the minimum creep rate was found to he an exponential for the two high-Qc processes and a power law for the low-Qc, process. Transition of control occurs from one mechanism to another. The relative transition temperature depends upon the applied stress, and the range oiler which the transition occurs depends upon the difference in the activation energies of the mechanisms. The creep behavior at high temperature is explained by the climb of dislocations through thermally or mechanically formed jogs, CREEP in pure fcc metals at temperatures in excess of one half the absolute melting point is normally controlled by dislocation c1imb.1,2 A climb model which seems applicable, according to an extensive analysis of data,3 was derived by Weert-man.4 This model assumes jog-saturated dislocations and predicts an activation energy, Qc, nearly equal to that for self-diffusion, USd. Although the requirement of jog saturation is restrictive, agreement between theory and experiment seems adequate. Many other theoretical treatments, including an early model by Mott,5 include detailed consideration of jog formation as an initial requirement for climb. These models predict activation energies for creep which differ from those of self-diffusion. Seeger6,7 postulates an observed activation energy related to the stacking-fault energy. Thus, Usd <Qc<5Usd + Uj where Uj is the jog-formation energy. Seeger incorporated qualitatively the influence of the relative numbers of thermal and athermal jogs. Expanding this concept, Shoeck8 explicitly states a function based on formation mode and relative numbers of vacancies: e r ci exp {-uf/k T} exp {-Um/k T} [ 1 ] where Uf and Um are energies of vacancy formation and migration, respectively. The concentration of jogs, Cj, depends upon the manner of jog production. For intersection jogs, Cj is not sensitive E. R. GILBERT, Junior Member AIME, formerly with De- to temperature; for thermal jogs, Cj is proportional to exp {—Uj /k T}. Schoeck regards each mode as a distinct mechanism; therefore, the mechanisms may act together.299 The diversity predicted by theory, surprisingly, has not been substantiated by experimental results. A significant investigation must include the extremes in stacking-fault energy. Extensive creep studies of aluminum10 and nickel,11,12 high stacking-fault energy metals, have been made. Comparable studies on a low stacking-fault energy metal, such as copper, have not. It is the purpose of this paper to report the results of an investigation of the creep of copper under conditions which favor thermal jogs. EXPERIMENTAL Cylindrical compression creep specimens (0.240 in. in diameter by 0.400 in. long) were machined from cold-drawn rods of electrolytic tough-pitch copper containing 0.0007 Mg, 0.002 Fe, 0.001 Ni, 0.0005 Ag, Cd < 0.005, and Pb < 0.005 wt pct impurities. Undetected spectrographically was a nominal 0.04 wt pct 0, which occurs as a Cu2O constituent distributed discontinuously at grain boundaries. Vacuum annealing at 900°C for 15 min produced a stable 0.03-mm average grain diameter. Testing was carried out using apparatus similar to that described by sherby,13 modified by enclosing platens and a push rod in a vacuum cylinder. Normally this arrangement resulted in pressures less than 10 Only a slight surface tarnish, less than 0.0005 in. in thickness, occurred during the test. The applied stress, corrected for atmospheric pressure, was maintained within 2 pct of the desired true stress by the addition of lead shot at fixed strain increments. Creep strain was measured with dial gages as a relative displacement of the upper and lower platens; accuracy of measurement was 0.0001 in. Two creep-test methods were used, the differential or cyclic temperature14 and the isothermal, to obtain creep data at stress levels of 150, 100, and 75 kg per sq cm over the temperature range of 620° to 1032°C. Minimum creep rates were used from both test methods; this was considered proper because comparable temperature tests or cycling to the same temperature gave the same creep rate, within experimental error. The cold vacuum test chamber, with the unstressed specimen in place, was heated to temperature by placing a preheated furnace over the chamber. Temperature equilibrium was attained within 30 min. For the cyclic tests, the stress was removed during the 5 to 10 min necessary to effect the temperature change and re-

Jan 1, 1965

By R. J. Brown

Design of a submarine pipeline system is governed by many factors, one of which is the effect of transverse horizontal currents on the pipeline structure itself Although this feature alone can be of utmost importance to the life span and stability of the underwater pipeline, it is usually the least recognized, with these hydro-dynamic forces being either completely overlooked or grossly underestimated. In an attempt to supply the methods and means for stabilization of sub-marine pipelines, much capital has been spent by pipeline companies. Design criteria incorporated by these organizations extend over a broad spectrum of engineering with bases varying from pure theory to cut and dry methods. A history of numerous failures has substantiated the postulate that many of these submarine pipelines have been underdesigned from the stability standpoint. By the same token, equally as many have been excessively overdesigned with resultant excess expenditures. An attempt has been made in this paper to establish the magnitudes of these hydrodynamic forces by measuring the lateral current-induced differential pressure distribution around the periphery of the submarine pipeline. INTRODUCTION The expenditure of money for research by corporations obviously requires beneficial results to justify the investment. One of the functions of the engineer is first to make the problem known and then to provide a means of solution at the least possible cost. The initial procedure is to investigate all pertinent published technical articles on the subject to determine if this problem has been previously solved. If resolution of this problem is not obtainable, the next course of action is to evaluate through experiments these forces and their magnitudes. On the specific subject of drag and lift, the accumulation of data is provided from three separate and distinct sources: from experience, from theoreticians and through experimental observations. The experience source has proved costly with money wasted either because of underdesign and failure or excessive expenditures for overdesign, and has not been sufficient to form a definite conclusion on these hydrodynamic forces. The pure theoretician is often not completely cognizant of the situation and his works bear little adaptation to the real problem. The experimentalist has his own problems with regard to obtaining results from small-scaled models and successfully adapting them to the larger prototypes. Each method has its own advocates who diligently adhere to their own separate routes as being the only means of resolving this problem. However, a review of the various methods of analysis leads one to the conclusion that if the advantages of all three are combined, a reasonable solution to this problem can be reached. Briefly then, the problem is to obtain the magnitudes of the forces on the submarine pipeline subjected to a lateral current by investigations of previous design considerations, by a study of existing theoretica1 data and by appropriate experimentation. This paper deals mainly with obtaining experimental data and the interweaving of theoretical and experience factors for resolution of these forces. APPARATUS AND PROCEDURE These tests were performed in 1961 at Collins Construction Co.&apos;s main office near Port Lavaca, Tex. Test equipment consisted of a steel tank 3 ft high by 4 ft wide by 40 ft long, with several pumps circulating the water through the tank via suction lines from the downstream portion of the tank and discharging from the pumps directly into the upstream end of the tank. For reduction of turbulence, a wire section was constmcted in the upstream portion and straightening vanes in the form of pipes, screens, etc., were used to reduce the vortex and eddy action in the tank (Fig. 1). A venturi was built at the test specimen for obtaining velocity sufficient to simulate actual conditions. This full-scale test was initiated to eliminate the error introduced in modeling and obtain a truer picture of forces actually encountered. Six- and 10-in. specimens were prepared by

Jan 1, 1967

By R. J. P. Lyon, A. E. Prelat, H. Lawrence

Introduction In 1977, the US Bureau of Mines awarded a grant to the state of South Carolina to explore the possibility of using Landsat multispectral scanner (MSS) data as an aid in monitoring surface mining activities in selected counties of the state. Work had been done in Aiken County prior to the grant by USBM and state personnel at the EROS Data Center using both the GE Image 100 and ESL IDIMS systems. The initial work on the 1:100 consisted of locating and measuring the areas of various kaolin mines. The results were excellent on location, identification, and accurate area measurements of several mines as compared with aerial photos of each mine. The effort also included locating and measuring the size of all mines (including sand and gravel) within two US Geological Survey (USGS) 7 % - min quadrangle maps. Line printer overlays using the IDIMS equipment and software resulted in the location of all known mines within an estimated error less than zt 91.4 m. Mine acreage was calculated by counting each symbol (which represented one pixel) and multiplying by 1.1 (the number of acres per pixel). [Fig. 1] shows a portion of one quadrangle overlay. [Table 1] gives a comparison of acreage measured for several mines from the 1-100 and IDIMS system vs. aerial photo measurements. The success of the preliminary work resulted in the South Carolina Land Resources Conservation Commission submitting a proposal to USBM for funding to expand the scope of work to other mineral mining operations within the state and determine if Landsat Imagery could be used to accurately locate and measure mining and reclamation activity on a continuing basis. Three separate tasks were proposed for selected kaolin mines in Aiken County: Task 1, to measure changes in active mine developments over the period 1974-77; Task 2, to measure reclamation activity, and, if time permitted, seasonal changes in mine signatures over the same period of time; and Task 3, to classify one complete mining operation (i.e., differentiate between active, spoil, overburden, water, reclaimed portions and surrounding terrain. The major effort was centered around J.M. Hubeis Richardson mine. Mining operations were progressing in a northerly direction and included three areas of reclamation: one prior to 1974; one started during early 1974; and one reclaimed during 1976. A discussion of all work done under the grant is available in the March 1979 Final Report listed under References. Computer compatible tapes (CCTs) containing MSS data from Landsat Path 18, Row 37, were purchased from the National Aeronautics and Space Administration (NASA) covering the period February 1974 through January 1977. The MSS data were processed on the General Electric Image 100 using parallelepiped classification at the EROS Data Center&apos;s Data Analysis Laboratory, Sioux Falls, SD, and at the Stanford Remote Sensing Laboratory, Stanford University, Palo Alto, CA, utilizing both an unsupervised classification (ISOMIX) and a supervised classification (sequential discriminant analysis). Studies at Stanford University Remote Sensing Lab (SRSL). In Feburary 1977, initial work was begun at Stanford using the STANSORT computer program running on a DEC PDP-10 (Honey, Prelat, and Lyon, 1974). This software is fully interactive and designed to study Landsat CCT data at high resolution (small areas) on a pixel-by-pixel basis (Lyon, 1977). Unsupervised Classification. The initial step was to locate the Richardson mine on the positive print of the full Landsat scene from CCT 1644-15252, dated 6/17/74. This was relatively easy due to a large abandoned kaolin mine and a long narrow pond clearly visible in the scene. Two unsupervised classifications of the Richardson mine were run using ISOMIX clustering (Honey, Prelat and Lyon, 1974). (ISOMIX essentially follows the interactive clustering procedures of ISOCLS Kan, Holley, and Parker. 1973). Although the classifications were successfully accomplished, it was apparent from the TV display that the results did not clearly define the mine areas. A supervised classification would have to be made in order to clearly separate each portion of the mine. Supervised Classification. This classification was done using the Stepwise Discriminant Program (BMDO7M) which is part of the BIOMED package (Dixon, 1970) and involved the following steps: Training group populations were selected and the digital

Jan 1, 1982

By Adrien Berton

FOR nearly a century, the Corocoro deposit has been renowned among geologists from the fact that it shares with the Lake Superior deposits of the United States the distinction of being the only important copper districts where native copper is worked commercially. The Corocoro district, named after the city of Corocoro, the capital of the Province of Pacajes (Department of La Paz, Bolivia) is situated towards the western edge of the Bolivian high plateau, at an altitude of a little over 13,000 ft. The most interesting part of the district is that immediately surrounding the city of Corocoro, at a distance, by railway, of 65 miles from La Paz and 210 miles to the Chilean port of Arica on the Pacific Coast. The climate of the region is that of the semi-desert, dry and relatively cold, with big differences of temperature between day and night. The rainy season begins in December and ends in March. The cupriferous lodes of Corocoro have not attracted as much interest as the silver mines of Potosi but they have been known for a long time. In the precolonial period the Indians were using the charquis, or natural native copper sheets, to make small brass objects, and the beautiful pale green brochantite of the outcrops as a source of green pigments. During the colonial period, the oxidized ores of the outcrops were worked for copper, which was used by the mint at Potosi for making currency. The native copper ores were neglected because the Spanish miners were at a loss how to concentrate and smelt them. About 1830, work by rudimentary processes, which were improved little by little, was begun on the native copper ores. The total production of native copper in the following hundred years amounted to 100,000 tons. This native copper, which was remarkably pure, was much appreciated on the European markets before the introduction of electrolytic copper. It was useful for making special ornamental brass or bronze and the granular concentrates of native copper, called barrilla, containing 80 to 85 per cent copper were suitable for making copper sulfate by direct oxidation and subsequent leaching with sulfuric acid.

Jan 1, 1936

By G. R. M. Del Giudice

A survey of the flotation literature of the past 10 years indicates an increasing use of the microscope as a tool for investigation. Thus, the metallurgical microscope has been used by Tucker and Head;&apos; Taggart, Taylor and Ince;2 Ince,3 and del Giudice4 to examine mineral surfaces that had been subjected to the action of various flotation reagents and to the action of slime pulps. It has also been used by Gaudin, Groh and Henderson;5 Martin;6 Morrow and Griswold;7 and others to examine bakelite briquets of mill products. The microscope with transmitted light, both with bright-field and dark-field illuminations, has been used by Taggart, Taylor and Knoll8 and by Ince9 to observe Brownian motrement and flocculation in flotation pulps. The use of the microscope at low-power magnifications with incident illumination for the examination of mill products has been known for years.10 Finally, del Giudice11 has used a relatively new type of illumination, the Ultropak, for the examinntion of slime-coatings.

Jan 1, 1935

By Persifor Frazer

The mines which I am about to describe are all situated in the northern part of the States of Nuevo Leon and Coahuila, Mexico, between the twenty-sixth and twenty-seventh degrees of latitude. They might be grouped, orographically, into four classes: 1. Those in the Sierra de la Ygnana chain; 2. Those in the Sierra de Gomez chain; 3. Those in the Cerro Mercado; 4. Those in the Sierra de San Marcos chain. (See large map.) The first two of these may be further arranged in one geographical district, to which the name, "the Villaldatna. district," may be applied, and the last may be ascribed to the geographical district of " Monclova." Geologically described, the country rock, in which four of the six mines occnr, is a limestone, concerning which a few words will be said further on, to wit.: The Arroyo (gulch), the Montanos and the Pinitos (pines), in the Villaldama district, and La Paloma (the dove), or Iron Mine, in the Monclova district. The San Rafael appears to lie in granite, or a heavy-bedded gneiss, presenting most of the characteristics of the latter, though the contact plane of the limestone is not far off. It is certainly worthy of attention that the ore occurs in that portion of the crystalline rock, which is nearest to the limestone, and it has been thought by some observers to be a true contact vein. It is well known that veins of this character are very often distinguished for constancy and richness. Although the undersigned cannot entirely free himself from the impression that this proximity of different formations has had an important influence in the origin of the part of the vein on which this mine is situated; still he was unable to establish it actually at the contact of the limestone and granite, but rather a short distance within the latter. Two openings of the Riojas vein were respectively in limestone and in rotten whitish granite, but this fact, if established (as by the correspondence of the strike line of the vein in direction with that of a line joining the

Jan 1, 1884

By John G. Tate, George W. Nicolson, James L. Bruce

For more than 25 years modern mining has been carried on in the Island of Cyprus, Mediterranean Sea, by the Cyprus Mines Corp. of Los Angeles, Calif. The general features of these operations have been described.&apos; From 1935 to June 30, 1940, top slicing in the Mavrovouni mine produced in excess of 2,000,000 long tons. The rate for the last part of this period was approximately 50,000 tons per month. Description of Ore Bodies The shape Of the Ore body now being top sliced in the Mavrovouni mine is an inclined irregular pyritic pipe or chimney of large dimensions) extending from unknown depths below the bottom level at elevation 250 ft below sea level) to the highest level at elevation 400 ft above sea level. The present surface above the ore body lies between 550 and 650 ft elevation. Undoubtedly the Ore body extended to surface and was Mined by the ancients by opencast and underground methods. The old pits were gradually filled up by erosion until now they show as slight depressions in the topography. The largest area of the Ore body is at elevation 170 ft below sea level, where the horizontal section is almost elliptical, with a width of 600 ft and a length of 1000 ft. Below this elevation the shape of the ore body continues to be elliptical but with reduced dimensions. Above this elevation it rises flatly towards the south with a substantial depression in the upper-side of the chimney and irregular ridges or wings rising on each side. It gradually grows smaller as it rises. The ore body is a pyritic replacement of andesitic extrusives which occur as flows and pillow lavas. With the exception of the upper portions of one or two small offshoots rising from the main ore body, all ore is completely surrounded by andesite. Most of the andesite lying above the ore body is covered by marl and Clay sedimentaries of Miocene and later age, The Miocene is presumed to be older than the ore mineralization. That portion of the andesites which lies between the sedimentaries and the ore body has been broken by slumpage, and weathered, and iron-Stained by the descending meteoric waters, It is a mass of crushed material that caves and follows downward readily as the top-slice stopes retreat. The main ore body is a heavy cupreous pyrites mass assaying on the average about 4.0 pet Cu; 48.0, S; and 42.0, Fe. In places the copper drops below 1.0 pet. on the borders of this heavy sulphide ore body lie disseminated cupreous pyrites ore deposits of large dimensions. some portions of these appear to be closely related to the heavy sulphide ore, as the ratio of copper to pyrite is about the same. The greater part of the disseminated ore, most of which lies immediately to the east of the main Ore body, contains less than 0.10 pct Cu and about 25.0 to 30.0 pct S. &apos;This probably can

Jan 1, 1949

By Paul Foote

MOST of the treatises on metallurgy intimate that simultaneously with the development by the atomic physicist of a really satisfactory theory of the atom will be inaugurated a new epoch in the science of metals. Metallurgically and metaphorically, we shall dwell in the Utopia of Sir Thomas More. It is my privilege this afternoon to demonstrate that this state has not arrived. An atom is a miniature planetary system consisting of a positively charged nuclear sun about which revolve electrons each carrying the negative charge e. The charge on the nucleus is + Ze where Z is the atomic number and the number of planetary electrons in a neutral atom is equal to Z. These electrons are arranged in several groups having different binding energies. Ordinary x-ray phenomena relate to processes occurring deep within the atom, usually with electrons in the so-called K or L shells. Such electrons in the heavier atoms are so closely bound to the nucleus that the forces exerted by neighboring atoms in a solid are relatively inappreciable. For most practical x-ray investigation, the atom may, be considered as in the gaseous phase completely isolated from its neighbors. The K radiation from an element in the gaseous state, in the solid or liquid phase, or even in combination with other elements in all its possible valences, is almost identical. ? Visual and ultraviolet spectroscopy is concerned with disturbances of the most loosely, bound outer or valence electrons of the atom, always in the vapor state. The remarkable progress of the last year in both theo-

Jan 2, 1926