Search Documents

By C. E. Sims, G. A. Moore

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949

By Alistair Frame

INTRODUCTION In April 1988 discussions were about to start with BP on the possibility of buying their- mineral interests, and it took a long time to arrange a deal. I will talk about RTZ without BP Minerals, look at the new RTZ with BP Minerals, discuss the outlook for metal prices, and review the problems in South Africa and develop the case against sanctions on that country. RTZAT THE END OF 1988 Late in 1987, after completing a worldwide review of our strategic thrust, we decided: 1. That the business focus would be to remain a major diversified natural resource group with interests in related industries. 2. To divest non-core and low growth businesses. 3. To develop a logical acquisition plan. 4. To emphasise organic growth and, most importantly, to enhance shareholders' wealth by capital increase and a progressive dividend policy. Subsequently, we concluded that we should sell our oil and gas business and dispose of several assets for which we saw little growth potential. The disposal programme raised some U.S.$ 1,600 million, representing a significant capital gain on our various investments. All transactions were carried out by our small Head Office staff in London, without the help of merchant banks and lawyers, and we were able to safeguard the employment of our staff in all these operations. The most interesting disposal was of our oil and gas interests. Before the 1987 strategic review, we had ambitions to develop our oil and gas interests and to become the leader in the second division of European oil companies. Our interests, which were purely in exploration and production of oil and gas, consisted of the 100% owned RTZ Oil and Gas company, and 29% of LASMO, a publicly quoted U.K. oil and gas company with extensive worldwide interests. LASMO, in turn, owned 25% of Enterprise Oil, one of the more successful of the North Sea oil exploration and production companies. Prior to the end of 1987, our intention was to acquire control of both LASMO and Enterprise. However, when we evaluated the net asset value of these two companies based on our oil price assumptions, which were pessimistic for the next five years or so, we concluded that they were both trading in the market at significant premiums. This, taken with the additional premium required for acquisition and the high cost of exploration, led us to conclude that, since funds could undoubtedly be used to better effect, we should sell our interests. Turning to the other major achievements in 1988, we commissioned, and built up to design levels in a very short period of time, the Morro do Ouro gold mine in Brazil. This mine reached its design output of 100,000 ounces of gold per year within three months of start-up, which was on time and under budget. We are now considering a possible expansion of this property. In South America, Utah International, Mitsubishi and RTZ arranged non-recourse finance, with post completion guarantees, for the giant Escondida Project in Northern Chile. Financing came from a group of banks in Japan, Germany and Finland -- the countries to which most of the concentrates will be sold -- and from the LEC. The average output of the mine for the

Jan 1, 1990

By Reinhardt Thiessen

In the general study of coal, all evidence points in the one direction —that coals had their origin in a manner analogous to that of peat. The best method of studying coal, whether it concerns its chemistry, composition, or physical condition, is to study peat. The essentials in a study of peat are a knowledge of the chemistry of plants, knowledge of decay and of the transformation process of plant-substances into peat. A number of facts must be emphasized, namely, (1) peat is formed under wet conditions only; (2) plants grow in the place where peat is formed; (3) all the plant substances go into the bog; and (4) all the plant substances are subjected to a series of phases of decay which are (a) in the air completely above the water level but in relatively moist conditions; (b) above the water level, but covered by debris; and (c) completely submerged by both water and debris. Plant Chemistry Plant chemistry as a whole is remarkably well understood. The number of compounds composing plants is large, and it is not possible here to give even a comprehensive outline, but a classification into definite groups is possible; this is as follows: Carbohydrates; glucosides; pigments; tannins; acids, alcohols and ketones, etc., and their salts; essential oils; resins; vegetable bases; proteins; enzymes. Plant substances may also be grouped according to the role they play in the life of the plant, such as: Framework materials, living materials, food materials, protecting materials, waste materials. While this classification groups them well for. certain purposes, it does not group them exactly chemically; but in a consideration of the composition of coal, this is an excellent classification for our purpose here.

Jan 1, 1925

By A. F. Giamei, E. J. Freise

A discussion of the various factors affecting the accuracy of volume fraction determination by the direct comparison X-ray diffraction method is presented. To minimize errors introduced by nonrandomization effects such as preferred orientation and large grain size, as well as errors introduced by statistical effects, an iterative mathematical analysis is introduced. This analysis is applied to all observable diffractio~ spectra from a given specimen by means of computer techniques and is statistically superior to the standard direct comparison technique which utilizes only one or tm sets of intensity spectra. The computer program also presents a graphical interpretation of- the results which enables the investigator to visualize and readily assess the scatter in volume fraction estimates caused by deviations from randomness. Finally, the iterative analysis is applied to experimental data collected from a series of plain carbon steels in both the as-received and spheroidized conditions to determine the volume fraction of cemen-tite present in each case. The results show markedly good agreement with chemical analyses for all spheroidized specimens. In theory, quantitative X-ray diffraction is a power-ful analytical technique for precise determination of the volume fractions of various phases present in a multiphase poly crystalline aggregate. There are two generally used methods; both utilize the fact that the intensity of a diffraction line of a particular phase is a function of volume fraction of that phase present in the aggregate. The more common method is the so-called internal standard technique where a known amount of standard substance is mixed with the aggregate containing the unknown. The resulting ratio of the intensity of a particular diffraction line of the unknown to the intensity of a diffraction line from the standard is used to find the weight fraction of unknown material by reference to the intensity data obtained from a previously prepared set of standards containing the same amount of standard material. The details of this technique are outlined in standard works on X-ray diffraction.' The disadvantages of the technique are that it requires the use of powder specimens and that the powder mixture must be homogeneous near the surface to the maximum effective beam depth. The alternative technique is the direct comparison method in which the ratio of the intensity of a diffraction line of a phase in the aggregate to the intensity of a second-phase diffraction line yields the ratio of the volume fractions of each phase present. This method has been applied most extensively to the determination of the percentage of retained austenite in martensitic steels and to determining the amounts of hcp and fcc allotropic modifications in pure cobalt5 and the amounts of hexagonal and rhombohedra1 modifications in graphite.8 This method is applicable to bulk as well as powder aggregates and is the technique which will be considered in the following text. It is the purpose of the present communication to show that by combining the results of X-ray diffrac-tometry with the use of high-speed digital computers the results of the direct comparison quantitative X-ray analysis technique can be optimized by using all of the data available on a diffraction pattern. THEORETICAL DISCUSSION In optimizing any quantitative X-ray diffraction experiment, the problem of accuracy vs time to collect and analyze the experimental data arises. For any method to be practical, it is required that both experimental and analytical procedures are reasonably short. In most of the previous work performed by the direct comparison method, intensity data from only one or two sets of peaks were used to calculate the volume fraction of phases present in the aggregate. Consequently, rather long-time experimental measurements are required to assure that the intensity data are sufficiently accurate to justify the use of one or two sets of data. By using computer techniques to analyze the experimental data it becomes feasible to use all of the available data on a diffraction pattern. By so doing, the time spent in measuring any one diffraction maxima can be appreciably reduced. Although this results in poor counting statistics for any one maxima, the number of data points available for analysis is greatly increased. Based on the above discussion, it will be assumed that a continuous scanning counter-diffractometer technique will be used to collect intensity data from a two-phase mixture. The integrated intensity of the ith diffraction line from the a phase in the aggregate is given by:'" where is the volume fraction of the a phase, The various quantities in Eq. [la] are angular independent while those in [lb] depend on the hkl spectrum of a particular phase. The meaning of the individual quantities in Eqs. [la] and [lb] are given in Appendix 1. It is convenient at this point to outline briefly the factors which will affect the measured intensity of any one hkl spectrum. a) Extinction effects arise from two independent experimental conditions. Primary extinction arises from a high degree of crystal perfection and results in spectra having lower intensity than predicted by Eq. [I]. Any treatment, such as powdering, which reduces

Jan 1, 1968

By W. Chubb

By measuring the hardness of metals at temperatures just above and just below their allotropic change point, it has been established that crystal structure has a real effect upon the strength of metals. The DPH of cobalt, iron, titanium, uranium, and zirconium have been measured at temperatures up to 1000°C. It was found that the body-centered-cubic crystal structure is always the softer structure when it is involved in an allotropic transformation. The close-packed and more complex structures are inherently harder, and may be expected, therefore, to be better base materials for high strength alloys. IT has been observed that for metals with nearly the same melting point (i.e., tin and lead, magnesium and aluminum) the metal with the more complex crystal structure has a higher tensile strength and hardness. It might be asked whether this effect is really caused by the difference in crystal structure; and, if so, just what is the contribution of crystal structure to the strength of these metals. A qualitative answer to these questions can be obtained by measuring the change in hardness produced by the change in structure in metals exhibiting allotropic forms. The evidence for changes in mechanical properties during allotropic transformations is rather meager. In 1909, Rosenhain and Humfrey' observed that "ß" iron showed much less deformation at the transformation temperature than a iron. By means of a torsion test, Lee found that iron bars were "critically plastic" at the a-7 transformation temperature. Sauerwald and Knehans have shown that the dynamic hardness of iron increases between 900" and 1000°C. In 1930, Albert Sauveur' presented data on the hardness, tensile strength, and torsional strength of pui-e iron up to 1000°C. He concluded, "At 900°C, the a iron transforms into y iron, and this is accompanied by increased strength and stiffness and decreased ductility." The same year, Schischokin" obtained data on the hardness of thallium at temperatures above and below its transformation temperature. His data are replotted on semilogarithmic coordinates as Fig. 1. The fact that his data fall on straight lines in this type of plot is believed to attest to the purity of his metal and the accuracy of his results. In 1941, Nadai and Manjoine" obtained tensile data on pure iron with an indicated increase in strength at about 900°C. These experiments make it quite evident that changes in mechanical properties occur when a metal transforms from one crystal structure to another; but, except for Schischokin's data on thallium, none of the measurements seem accurate enough to determine the relative magnitude of the mechanical property change. Materials The metals that have been examined for changes in hardness during transformation include l—as- deposited commercial electrolytic cobalt about 99.7 pct pure, 2—Armco ingot iron, 3—are-melted iodide titanium of a purity in excess of 99.8 pct, 4—uranium of a purity in excess of 99.5 pct, 5—are-melted iodide zirconium of a purity in excess of 99.8 pct, 6—annealed, 0.08 pct C, rimmed steel, and 7—commercially pure RC55 titanium. While the purity of the first five of these materials leaves something to be desired, it will be noted that the observed hardness discontinuities occurred at the accepted transformation temperatures. (These temperatures are indicated by vertical arrows in Figs. 1 and 3 through 7.) The last two materials are commercial alloys introduced to show the effect of minor alloying elements upon the hot hardness curve. Apparatus Hardnesses at elevated temperatures were determined by means of a vacuum hot hardness machine. A diagram showing the basic features of this machine appears as Fig. 2. This machine is essentially a deadweight hardness .machine in a furnace within a vacuum chamber. The sapphire-tipped indentor

Jan 1, 1956

By Robert J. White

Strong's equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong' published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong's paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By R. E. Boni, G. Derge

SURFACE tensions of molten silicates are of metallurgical importance for many reasons. From a knowledge of their values, an insight into the problem of liquid slag structure can be gained. Also, such problems as separation of slag from metal, slag penetration of refractories, spreading of enamel coats on metals, bonding of cutting wheels, adsorption of gases, frothing of slags, and homogen-ization of slags are related to the surface tensions of the silicates. Because of the absence of a correlated review of the work that has been conducted in this field, the following survey is presented. It is not a complete summary of all the surface tension studies of silicates but only a review of the literature which is pertinent to metallurgical applications and research. Liquid Surface Tension The surface of a liquid differs from the interior in that its particles (ions, atoms, or molecules) are not

Jan 1, 1957

By R. Dawson Hall

WHAT are the opportunities for the services of engineers in the coal mines? The best answer perhaps can be made by detailing the present lines of development in the bituminous coal mining regions. They are just at the beginning of a period that can be conservatively termed revolutionary. A few glimpses of new possibilities in economic mining that will reduce the cost of bituminous coal at the mines by at least one half have convinced almost everyone that a change must shortly come about. The cost of housing has become such a burden, especially in mountainous regions, that development which demands the hiring of more men and constructing more houses would not be profitable. The introduction of mechanical aids to mining, transportation and dumping suggests a way of obtaining a large tonnage with the same or a smaller number of men with no further house construction. At the same time the restriction of immigration has made it increasingly difficult to obtain men inured to hard labor. Modern civilization is not productive of muscular energy and at the same time it provides men who are not indisposed to the use of the mental effort required to direct the physical forces now available for the replacement of such energy.

Jan 1, 1924

The following is an incomplete list of members and guests who called at Institute headquarters during the period Feb. 10, 1919, to Mar. 10, 1919. R. H. Allport, Cleveland, Ohio. R. R. Landon, Philippine Islands. I. H. Bergstein, New York. Alfred 0. Law, Cambridge, Mass. Capt. R. S. Burdette, San Antonio, Tex. James M. Little, Towanda, Pa. William R. Chedsey, State College, Pa. F. E. Marcy, Salt Lake City, Utah. L. R. Clapp, Philadelphia, Pa. H. F. Nash, Bartlesville, Okla. J. Murray Clark. L. S. Panyity, Columbus, Ohio. E. H. Claussen, San Francisco, Calif. W. C. Ralston, Reno, Nev. George E. Collins, -Denver, Colo. T. A. Rickard, San Francisco, Calif. George L. Collord, Sharpsville, Pa.. W. A. Rigby, Mt, Vernon, Iowa. William M. Corse, Mansfield, Ohio. H. H. Rowatt, Ottawa. Frank R. Crampton, Los Angeles, Calif. P. H. Royster, Pittsburgh, Pa. Capt. E. 0. Daue. Alan B. Sanger, Dorchester, Mass. A. E. Eddy, Butte, Mont. J. S. Shaw, Pittsburgh, Pa. N. H. Emmons, 2d, Lynchburg, Va. S. B. Shutts, Lynchburg, Va. E. W. Engelmann, Hayden, Ariz. Henry B. Smith, New Britain, Conn. F. A. Fahrenwald, Cleveland, Ohio. W. C. Smith, Roselle, N. J. 0. S. Finnie, Ottawa. Harry M. Spoor. John T. Fuller, Honesdale, Pa. D. M. Stackhouse, Johnstown, Pa. Major C. C. Griggs, Eureka, Utah. F. D. Stay,. Cleveland, Ohio. H. F. E. Gamm, Rutherford, N. J. D. B. Sterrett, St. Cyr, Que. A. W. Hackwood, Butte, Mont. R. H. Thayer, Yonkers, N. Y. C. L. Horne, Roanoke, Va. Kirby Thomas,. New York. B. B. Hood, Chrome, N. J. Henry Traphagen, Toledo, Ohio. R. E. Hore, Toronto Ont. H. D. Trounce, San Diego, Calif. Ross B. Hoffmann, Oakland, Calif. Henry J. Volkin, Ossining, N. Y. G. A. Joslin, Salt Lake City, Utah.. A. T. Ward, Bellefonte, Pa. John Johnston, Washington, D. C. Major L. W. Wickes. Paul S. King, Wilmington, Del. Horace V. Winchell, Minneapolis, Minn. E. William Kohl, Jr., Philadelphia, Pa. Fred L. Wolf, Mansfield, Ohio. W. H. Landers, San Francisco; Calif. J. Carson Adkerson, of the Stockwood Realty Corpn., Inc., of Woodstock, Va., writes that they are discontinuing their operations in Virginia on account of the conditions in the manganese market following the end of the war.

Jan 4, 1919

By W. R. Crane

THE effect of mining in the red-ore mines of the Birmingham district has been observed for some time, but, except in a few localities, little difficulty has been experienced from disturbance of cover. Cave-ins near the outcrop and fracturing of the surface at greater distances are the most pronounced manifestations of disturbance, while limited areas at points distant from the outcrop and under greater depth of cover have actually subsided. There is no doubt but that in time, because of failure of pillars, extensive fracturing and widespread settlement of the surface will result, particularly along the slope of Red Mountain, where mining has been under way for many years. Were it not that the orebed is overlain by one or more water-bearing formations, the fracturing or settlement of the surface would not be serious; but because of these formations, fracturing of the top rock may in itself be of sufficient importance to warrant the adoption of protective measures. Until development openings and surface plants are transferred to Shades Valley, protection of the surface will probably not be considered imperative, as the area involved is not of particular value for agricultural or building purposes. Further, the collapse of pillars over a wide area may develop squeezes that, if not controlled, may jeopardize the integrity of the mines and necessitate a change in development, from slopes to vertical shafts, at a much earlier period than is now contemplated. The occurrence of heavy beds of strong tough materials at varying distances above the orebed make it doubtful whether any serious disturbance of the surface will be experienced at any considerable distance from the outcrop, although some settlement will probably take place. It is certain, however, that no great volume of water will enter the mines from fracturing of the Fort Payne chert bed, as this is known to be a compact and practically impervious formation beyond the leached zone. Not so much can be said, however, regarding other possible sources of water, as pervious beds and through faults that may be encountered in future mining operations.

Jan 8, 1925

By S. Leber, R. F. Hehemann

Diffusion coefficients for the Cb-W system were measured using couples prepared from poly crystalline, commercially pure metals. The diffusion coefficients, measured in the temperature range between 1700° and 2300°C, decreased exponentially as the tungsten concentration was increased from 0 to 50 at. pct, then decreased abruptly at higher concentrations. A decrease of two orders of magnitude was observed over the entin? compositional range. The diffusion coefficients were in the range defined by the self-difiusion coefficients of the individual elements, indicating their general validity. An activation energy of 60,500 cal per mole was measured for the 20 pct W composition. Such low values, when compared with energies over 100,000 cal per mole for the pure constituent elements, indicated that transport mechanisnzs more rapid than volume diffusion were contributing substantially to inter dijfusion. Difference should, therefore, be expected between these data and the intrinsic diffusion coefficients. These differences should be significant in the kinetics of 'transport phenomena in practical systems. CONSIDERABLE attention has been devoted in recent years to the mechanical behavior and other properties of the refractory metals and their alloys. The Cb-W system has been of special interest as a base for the development of more complex compositions of commercial interest. In spite of the importance of mass transport to all aspects of elevated-temperature behavior, and especially to the production of alloys by powder-metallurgy techniques, little attention has been paid to diffusion in the Cb-W system. Results from a previous study of this system1 appeared to be anomalously high. The present investigation is, therefore, an attempt to obtain more accurate diffusion coefficients in this system. Intrinsic diffusion coefficients, of primary importance from the theoretical viewpoint, can only be obtained accurately from studies utilizing compositional gradients approaching zero. However, many practical problems involve diffusion under significant concentration gradients. The diffusion coefficients determined in this investigation were, therefore, obtained from couples prepared from elemental metals. The data obtained should be of value in the analysis of problems such as homogenization during powder-metallurgy alloying or reactions between base and clad in coated structures. In this vein, the investigation was conducted on poly crystalline materials of commercial purity. PROCEDURE Diffusion couples were prepared by sandwiching a columbium sheet between two sheets of tungsten. The composite was welded around all edges, the tungsten forming a protective can for the columbium. The composite was soaked for 4 min at 1600°C in a hydrogen-atmosphere furnace, quickly forged to 40 pct reduction in thickness, and then rapidly cooled to room tempera-

Jan 1, 1967

By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948

By M. S. Burton, G. V. Smith, A. Rosen

The kinetics of re crystallization and the effect of recovery on recrystallization of pure iron were investigated within the temperature range of 517" to 632 OC. Grain growth and activation energies were also studied. Two stages can be distinguished during recrystallization; the first is gvowth-controlled and the second is nucleation-controlled. The extent to which the first stage succeeds before the second stage begins depends on both temperature of recrystallization and temperature of recovery. The softening of cold-worked metals and alloys due to transformation of the deformed crystals to strain-free equiaxed grains during annealing is well-known, and early inestiators established that recrystallization kinetics is strongly influenced by minute quantities of impurities. Generally, it is believed that impurities decrease the rate of recrystallization and the rate of grain growth. To understand the basic phenomena of recrystallization, investigations should be on pure materials. Most of the research on high-purity materials has been on metals having the fee Bcc materials, and especially high-purity iron, have been studied only in recent years. It is known that recovery may influence recrystalliation;" however, no general description of the influence, applicable to all materials, has been presented. This paper presents results of a study of the recrystallization kinetics of high-purity iron, after 60 pct cold deformation by drawing, with particular reference to the influence of recovery on the rates of recrystallization and grain growth. From observations of these rates, conclusions are drawn concerning nucleation. MATERIAL AND EXPERIMENTAL PROCEDURE Preparation of Material. High-purity iron, prepared by zone refining of vacuum-melted electroiytic iron at Battelle Memorial Institute under sponsorship of the American Iron and Steel Institute, was used in this study. Table I gives the reported chemical analysis of the material, taken at a point near the last molten zone and thereby rep- resenting the maximum impurity level for the entire bar. Prismatic specimens, approximately 10 x 10 X 50 mm, were sawed from the 50-mm-diam bar, perpendicular to the zone-refining direction, and turned to cylindrical shape. These specimens were sealed in quartz capsules under vacuum, approximately 10"e mm Hg, austenitized at 930° C for 15 min, slowly cooled, removed from the capsules, and cold-worked in air by swaging to approximately 20-pct reduction of area. The encapsulating, austenitizing, and swaging operations were repeated two additional times, after which the samples were encapsulated, austenitized, and cold-drawn to 60-pct reduction of area. A further vacuum anneal at 630°C for 120 min and cold drawing to 60-pct reduction of area produced wire 2.8 mm in diameter. The drawn wire was electropolished to remove deformed material on the surface, after which it was sawed into 4-mm-long specimens for the recrystallization study. Microscopical examination before the final cold reduction revealed equiaxed grain structure with very fine grains in a thin layer near the surfaces of the specimen and nearly uniform ASTM 3-4 grain size in the center. Recrystallization Heat Treatment. a) Direct Recrystallization of Cold-Worked The 60 pct cold drawn iron specimens were recrystallized at five temperatures, 517, 556, 590°, 612, and 632C, in a lead bath covered with graphite (the temperature was controlled to 1°C). Specimens were treated for twelve different times at each temperature, and all were water-quenched after heat &eatment. b) Recrystallization Following Preliminary Recovery Heat Treatment. After cold working, specimens were sealed into quartz capsules under vacuum, 105 mm Hg, and recovery-annealed at 362", 400", and 440°C for 20 hr prior to recrystallization. No evidence of recrystallization was found

Jan 1, 1964

By R. D. Reiswig, J. M. Dickinson

The 0s-Ir equilibrium diagram was determined. The diagram is of the simple peritectic type, with a peritectic temperature of about 2660°C. The solid miscibility gap is narrower than previously reported, the nearly vertical solvus lines occurring at about 42 and 63 wt pct 0s. Widmanstaetten figures resembling martensite in some of the two-phase alloys account for a previously suspected transformation. In view of the long history of use of such alloys, it is surprising that the 0s-Ir equilibrium diagram has not yet been completely determined. The boundaries of the miscibility gap in this system have been estimated to be between 24 and 39 wt pct 0s and 79 and 100 wt pct OS. It has been predicted3 that alloys of ruthenium, osmium, and rhenium with the fcc platinum metals should solidify peritectically in their two-phase regions. The metallographic examination of natural osmiridium alloys has been said4 to indicate, by the presence of a martensitic structure, the existence of a transformation or a phase separation. On the basis of superconducting transition temperature measurements, a 70 at. pct 0s alloy was found5 to be two-phase prior to annealing. EXPERIMENTAL The elemental components used in this work were obtained from several suppliers as sponge. The purities, stated by each supplier to be in excess of 99.8 pct, were confirmed in each case by a semiquantitative spectrographic analysis. The pure components were premelted in an inert-gas tungsten arc furnace with the evolution of some fume, crushed, and pickled for use as alloy melting stock. Upon arc melting to the final compositions, no fume evolution was observed. Because weight losses of the order of 15 mg or less were observed in preparing alloy buttons weighing 15 g, "synthetic analyses" were used in determining the compositions of the alloys. Alloys used in this investigation contained 15, 20, 33, 40, 42, 43, 45, 50, 55, 60, 63, 64, 66, 70, 79, and 80 wt pct 0s. Heat treatments of the alloy buttons and pieces thereof were performed in a previously described6 tungsten tube furnace under pressures of 105 torr or less. It was found that homogenization treatments on the specimens were essential to remove the severe coring which was present, a 3-hr treatment above 2300°C removing all the metallographi-cally visible evidence of coring. Following the various heat treatments, the specimens were "vacuum-quenched" by melting a tungsten fuse wire and allowing them to drop onto a water-cooled copper plate. In a few instances, specimens were quenched into molten tin for comparison, but no difference was apparent. Vacuum-quenched specimens cooled from 2400°C to below a red heat in less than 60 sec. Typical equilibration times varied from 3 hr above 2300°C to 88 hr near 1100°C. The utilization of successively longer equilibration times and the approach to equilibrium from both directions indicated that the times used were sufficient to give a close approach to true equilibrium. Heat-treatment temperatures were measured with a calibrated Leeds and Northrup optical pyrometer through a 0.120-in. lateral sight hole in the tungsten heater tube. It was known that the assumption of black-body conditions inside the 1-in.-diam by 10-in.-long tube was unwarranted. The empirical results of work with thermocouples and melting

Jan 1, 1964

By Dick Whittington, W. R. Taylor

GENERAL In mid-1974, a representative of ARCO Petroleum Company walked into our Austin offices and asked for a permit for ARCO's first Clay West Mine site. This was the first in situ uranium mining permit issued in the United States. That initial permit, issued in January 1975, was for three acres. The four years since have been characterized by growth and change. Today there are 16 permits approved for approximately 1,540 production acres issued to five companies at eight sites in four counties. There are approximately seven additional permit applications being processed or on the verge of being submitted for an estimated 2,000 additional acres of production. As a rough gauge of the financial scope of this activity, at the typical 40 production wells per acre and an estimated $2,000/well, operators hale installed or committed $122 million for production wells. This does not account for the exploration and development wells installed to delineate the ore or the cost of processing facilities for extracting the uranium. HISTORY OF URANIUM MINING IN TEXAS Information I have concerning early in situ uranium mining activities is "sketchy" but the apparent first on-site test of in situ uranium mining was conducted between 1967 and 1971 at the Dueterstat site, north of Yorktown in Gonzales County, by City Service. Others ran tests at the Bruni site in Webb County and the Burns and Clay West sites in Live Oak County in the mid-70's. During this period, Texas Water Quality Board personnel in the central and district offices maintained a general surveillance of these various test activities. Regulation of in situ uranium mining was formalized with the issuance of a permit in January 1975 with the advent of ARCO's initial production scale (3 acre) effort in the Clay West area at the Moser mine site. Since 1975, the accelerating rate of mining and exploration activity is noticeable. There were 16 exploratory rigs operating early in 1977. This year, the rig count is averaging 46--a 287% increase. HISTORY OF LEGISLATION Paralleling this mining activity was state and federal legislation which subjected in situ mining to environmental regulation. The following is a brief chronology of the legislation that is directly or indirectly related to uranium mining. As most of you know, disposal wells are an integral part of most in situ uranium mines operating in Texas. They are used both during production and during aquifer restoration following production. The wells are regulated by the Texas Injection Well Act, enacted in 1961 by the Texas Legislature. In 1967, the Water Quality Act established the Texas Water Quality Board, and provided for the regulation of water quality by the so-called permit system. In 1969, the Solid Waste Act was enacted by the Texas Legislature. The legislation provides for control of wastes from manufacturing, mining, and agriculture. This Act regulated uranium surface mining activities until 1975 when the Texas Surface and Mining Reclamation Act placed responsibility with the Railroad Commission for uranium open-pit mining and surface mining of coal and lignite. In 1972, the Federal Water Pollution Control Act (Public Law 92-500) was passed. This legislation forms the legal base for the NPDES (National Pollutant Discharge Elimination System) and the subsequent point source effluent guidelines and standards. The November 6, 1975 issue of the Federal Register published interim final rules for Best Practical Treatment levels for effluent discharges from ore mining and dressing operations. Litigation was immediately initiated by eleven companies against these proposed rules, and they are currently being reconsidered for reissuance in 1979. In 1974, the Federal Safe Drinking Water Act (Public Law 93-523) was enacted. A part of this legislation is the Underground Injection Congrol Program. The regulations implementing this program have undergone various public hearings and it is expected that they will be published in the Federal Register before the end of 1978. In 1975, the Texas Surface Mining and Reclamation Act (Senate Bill 55), providing for the Railroad Commission's authority to require reclamation of surface mines, was passed. In 1977, an amendment to Senate Bill 55 was introduced that proposed to place regulation of in situ mining of coal, lignite, and

Jan 1, 1979

By A. H. Daane, R. L. Myklebust

The yttrium-manganese system has been investigated by thermal, metallographic, and X-ray diffraction methods. There are three intermetallic compounds present: YMn2 which melts congruently, YMn4, which undergoes syntectic decomposition, and YMn,, which undergoes peritectic decomposition. The compound YMn4 is ferromagnetic at room temperature with a Curie temperature of 214°C. There are eutectics at 25.2, 60.9, and 82.0 wt pct Mn which melt at 878°, 1100°, and 1075°C, respectively. Crys-tallographic data are given for YMn4, and YMn12 . The terminal solid solubilities are low. In a general program of study of yttrium metal in this laboratory some alloy systems of this metal with elements of the first transition period have been examined. This work was originally instigated by experiences in cladding yttrium with jackets of some protective metals such as Inconel for high-temperature service in air.' In some cases a low-melting phase was observed to form between the Inconel and the yttrium resulting in failure of the samples. In characterizing this reaction, a survey was made of the systems of yttrium with chromium, manganese, iron and nickel,, and it was found that a eutectic was formed between these metals and yttrium on the yttrium-rich side of the system. This present study of the Y-Mn system was carried out to examine in more detail the alloying nature of yttrium, and to correlate trends that have been observed in previous related studies. It was observed by Voge13 that in the systems of lanthanum, cerium, and praseodymium with each of the metals in the first transition series, the tendency to form compounds diminished in the order nickel, cobalt, and iron while no compounds were formed with manganese, chromium, or titanium. Beaudry and Daane4 observed a similar behavior in the systems of yttrium with some members of the first transition series except that the tendency for compound formation was greater. Both the Y-Ti5 and Y-Cra systems consist of simple eutectics, while in the Y-Fe,7 Y-CO, and Y-Ni4 systems, there are four, eight, and nine compounds, respectively. In addition to the above trends, the similar atomic radii and electronegativities of yttrium and thorium invite a comparison between their alloying behaviors with a common element such as manganese. In crys- tallographic studies, Florio et al.' have identified three intermediate phases in this system which are ThMn2, Th6Mn23, and ThMn,,. Gschneidner and Waber10 have examined published information on alloy systems of the rare-earth metals and have correlated this information with current alloying theory. From their study, they predicted that the Y-Mn system would contain one intermetallic compound. On the basis of this prediction, the trend in the alloying behavior of yttrium with the elements of the first transition series and the alloying behavior of thorium with manganese, one might expect from one to three intermetallic compounds to form in the Y-Mn system. A consideration of Hume-Rothery's rules of alloying based on size-factor, electronegativity, and valency suggested a small terminal solubility and possible compound formation. The present study was undertaken to confirm these predictions of low terminal solid solubility and compound formation and to establish the general alloying behavior of yttrium with manganese. EXPERIMENTAL Materials. The manganese used in this investigation was obtained from the Foote Mineral Co. as electrolytic plates of 99.9 pct stated purity; the yttrium metal was prepared in this laboratory. Table I gives the analyses of these materials. For the solubility studies at the yttrium-rich end of the alloy system, distilled yttrium, whose major impurity was 200 ppm Ti, was used. Preparation of Alloys. The alloys were formed by comelting the two metals in an are-melting furnace under an atmosphere of argon. The buttons thus formed were inverted and remelted three to five times to promote homogeneity. Due to the high vapor pressure of manganese, it was assumed that the weight lost during are-melting was all manganese. This assumption was based on the very good agreement observed between calculated compositions and chemical analyses of several alloys. The compositions of the dilute alloys used for solid solu-

Jan 1, 1962

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.'-4 Samsonov et al.' reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami's Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps : 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. .These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the molecules will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1964

By Erhard Hornbogen

Twins were propagated into large, well-annealed crystals of a, iron-phosphorous and a, iron-molybdenum solid solutions. Strain fields caused by interaction of these twins were made visible by precipitation. These strain fields can be explained by assuming that transmitted and reflected plastic waves are created when a twin strikes an obstacle with high velocity. The twin front itself can be regarded as a shear wave that may be able to develop a one-dimensional shock front. The occurrence of {WO} fracture by the reflected stress is also discussed. The described effects were not found when twins propagated at lout velocity into disturbed crystals, for example, into crystals previously deformed by slip. DEFORMATION twinning leads to shearing of a crystal lattice under external load. The shear appears to be homogeneous over a large number of crystal layers. In a iron, shear occurs on the (112) planes and in the <1ll> directions. The formation of a twin proceeds by the movement of partial dislocations that change the stacking at the twinning plane.l, In the bcc lattice, this partial dislocation can be created by dissociation of a sessile a/2[111] dislocation that lies in the (112) plane: Cottrell and Bilby&apos;s spiral mechanism can explain the homogeneous shear, but has not been proven experimentally. Nevertheless, this mechanism can explain the possible high velocity of formation of a twin. In Cottrell and Bilby&apos;s model, as in other models of twinning or phase transformation, a much higher energy is required to spread the first stacking fault than to add new layers by further movement of the partial dislocations. The dislocations will therefore become accelerated proportional to the difference between the stress, tN, to nucleate and tp to propagate the twin. It has been assumed3,4 that tn is the stress required to make two partial dislocations of apposite sign pass for the first time. After the first layer of new stacking has been formed, the maximum stress is TN=Gb/4pd where G is the shear modulus, b is the Burgers vector of the partial dislocation, and d is their perpendicular spacing so that the amount of shear is S = b/d. From this formula, a value of 25 kg per mm2 has been estimated for twinning in Zn3. The measured values are smaller, but local internal stresses may help to provide the necessary stress. For a iron, a higher value can be expected, mainly due to the higher value of G. That agrees with the observation that "burst" twinning occurs if the yield strength is in-

Jan 1, 1962

By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948