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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 R. H. Hawkins

An investigation of the applicability of geophyiical methods to northern Ontario lignite deposits was undertaken early in 1930 by the Ontario Research Foundation at the request of the Ontario Department of Mines Pre-Cambrian ... Syenite, granite gnciss, etc. Igneous intrusivcs . Lamprophyre dikes cut the Abitibi River and lover formntions. (Permission of Ontario Dept. of Mines) and was financed in part from a research grant made by the latter organization. The work to date has included gravitational, magnetic and electrical resistivity studies. The gravitational and magnetic measure-

Jan 1, 1934

By Charles T. Holland

In connection with the problems of bumps in coal mines, much has been written concerning the manner in which roof action and methods of mining enter into the pressure effects observed but little has been written upon the relationship between the physical properties of coal and associated rocks and the cause of bumps. The question of the strength of bituminous coal, of its elasticity, and the energy it can absorb and store has been neglected to a considerable extent in connection with this problem. It is generally agreed that one of the necessary conditions for bumps is a strong coal.' Therefore, since the strength of coal is an important factor, a study of this property should be made. several investigators have conducted laboratory experiments upon the strength of coal, using small cubical or rectangular test pieces. An attempt will not be made to go into all of these investigations, but they are briefly summarized in Table I. Experiments of the U. S. Bureau of Mines and of Lawall and Holland (pp. 27 and 34 of ref. 9), however, indicate that regardless of whether the coal is a soft and weak semihituminous (Pocahontas No 3) or a hard and strong bituminous (Stockton) coal, the maximum ultimate unit stress developed in laboratory tests is higher in small cubes than in larger cubes of the Same coal.

Jan 1, 1942

By Charles T. Holland

In connection with the problems of bumps in coal mines, much has been written concerning the manner in which roof action and methods of mining enter into the pressure effects observed but little has been written upon the relationship between the physical properties of coal and associated rocks and the cause of bumps. The question of the strength of bituminous coal, of its elasticity, and the energy it can absorb and store has been neglected to a considerable extent in connection with this problem. It is generally agreed that one of the necessary conditions for bumps is a strong coal.' Therefore, since the strength of coal is an important factor, a study of this property should be made. several investigators have conducted laboratory experiments upon the strength of coal, using small cubical or rectangular test pieces. An attempt will not be made to go into all of these investigations, but they are briefly summarized in Table I. Experiments of the U. S. Bureau of Mines and of Lawall and Holland (pp. 27 and 34 of ref. 9), however, indicate that regardless of whether the coal is a soft and weak semihituminous (Pocahontas No 3) or a hard and strong bituminous (Stockton) coal, the maximum ultimate unit stress developed in laboratory tests is higher in small cubes than in larger cubes of the Same coal.

Jan 1, 1942

By Armando M. Lago

Secular and cyclical patterns of postwar sources and uses of funds of the mineral sector are analyzed. A simultaneous equation behavior model of sources and uses of funds is developed for both mining firms and integrated producers, and these models were put through the task of predicting the financial and expenditure be-havior of mineral corporations in response to mergers and changes in investment tax credits and depletion allowances. Finally, the quantitative analysis methodology is applied to the analysis of optimum capital structure of mining corporations. The postwar changes that have occurred in the expenditure and financial behavior of mineral corporations are reviewed, particularly the relative importance of factors that affect the industry's supply and demand for funds. This quantitative statistical investigation of factors affecting sources and uses of funds of mineral corporations is achieved through the formulation of a simultaneous equation model of sources and uses of funds. After a description of the study sample, the postwar cyclical and secular financial behavior of mineral corporations is analyzed in detail. An econometric model of mineral corporate financial behavior is formulated. This model is then estimated and reviewed. Policy issues regarding depletion allowances, investment tax credits, and industrial organization of the mineral sector are discussed. Finally, the optimum financial structure of mining firms is discussed and the effect of corporate financial structure on the mining corporations' average cost of capital is analyzed.

Jan 1, 1971

By W. H. Emmons

This paper is the third of a series treating of the relations of ores of the metals to igneous rocks. The first' outlined the general problem; the second2 proposed a classification of lode ores, and showed how the distribution of the deposits is in a certain measure controlled by the contour of the roof of the parent batholith. A number of mining districts were discussed, the examples being selected chiefly from group 2 of the classification. The proposed classification of lode deposits, briefly stated, is as follows: 1. Cryptobatholithic: near hidden batholiths which have not yet been exhumed by erosion. 2. Acrobatholithic: in and near cupolas or domes of batholiths—the high points of larger underlying masses. 3. Epibatholithic: on batholiths, near their rims, but below eroded cupolas, or below the highest points of the roofs. 4. Embatholithic: among closely-spaced outcrops which probably are parts of a single bathohth. The outcrops of invaded rocks predominate. 5. Endobatholithic. in and near roof pendants of large batholiths. The invading rocks predominate. 6. Hypobatholithic: in deeply-eroded batholiths, where even roof pendants have been eroded. Deposits of certain metals on the roofs of the batholiths are much more numerous in some positions than deposits of other metals, and the horizontal zonal arrangements of lodes of different metals are shown characteristically only in certain groups. In a large measure, also, the character of the fracturing and metallization is determined by the position on the roof of the batholith. The disseminated copper ores in porphyry constitute a clearly-defined type. All the deposits of these ores, as far as known, are in group 2. They appear to have been formed only in and around small upward projections of the parent granitic masses, and not low on the walls of the

Jan 1, 1927

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.' The porous-pellet model is found to give a better description than the dense-pellet one for McKewan's measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.''' However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.' One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed' to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By T. C. Campbell

Copper is extracted from the Chuquicamata oxide ore by a hydro-metallurgical process. The ore is crushed to 3/8-in. sizing, and leached with a sulfuric acid electrolyte. Chlorine is precipitated. and the ferric iron reduced in the enriched electrolyte, after which the copper is recovered by electrolysis with insoluble Chilex and lead-antimony anodes, the spent electrolyte being returned to leaching. Cathodes are melted and refined in market furnaces and cast into commercial wire-bar and cake shapes. Sulfuric acid for the process is supplied by the brochantite in the ore. Water for washing the ore is advanced through the solution system and finally after cutting by electrolysis to from 6 to 16.0 grams per liter is completely stripped by the cuprous chloride method and run to waste. The cuprous chloride so obtained plus that resulting from precipitation of chlorine from strong solution is dissolved in ferrous chloride brine and the copper cemented on scrap iron. The cement so obtained is in part used to reduce ferric iron in electrolyte, and as it is of exceptional purity is also furnace refined and cast into an exceptional quality of fire-refined copper. Fig. 1 is flow sheet of the operation. The reduction plant is composed of seven divisions as follows: (1) crushing, (2) leaching, (3) tailings disposal, (4) dechloridizing, (5) sulfur dioxide treatment, (6) electrolytic tank house, (7) smelting and melting. A brief description of each of these divisions will be given. Crushing Ore that is frequently blocky and up to 5 ft. in section is crushed in four stages to 3/8-in. mesh. The first stage of crushing is called primary and the next three stages are known as secondary crushing. The first stage is accomplished with two 60-in. Superior McCully gyratory breakers by which the ore is broken to 9 in. The second coarse gyratory breakers crush the ore to 3-in. sizing. There are seven No. 10 McCully gyratories in this service, for one of which recently has been substituted a No. 7 cone crusher. The third and fourth stages of crushing are accomplished by fifty 48-in. disk crushers. In the third stage 14 disk crushers break the ore to 1 in., and in the last stage 36 disk crushers turn out the final product of 0.371-in. sizing. Reference to the flow sheets of Figs. 2 and 3

Jan 1, 1934

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By John Chipman, Theodore B. Winkler

IN order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chipman,3 dealt with the simplest possible slag system that would resemble those found in the basic open hearth-the slag system consisting of CaO-MgO-SiO2-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemistry of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, Si02, FeO, Fe203, P205, MnO, A1203 and CaF2, but not all of the slag samples contained all of these components at one time. REVIEW OF LITERATURE Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Brings4' von Samson-Himmelstjerna,5 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution ratios

Jan 1, 1946

By D. F. Gibbons

THIS investigation was undertaken in order to gain further information on the mechanism of plastic deformation of iron at temperatures between room temperature and 77.2°K, and also to contribute to our understanding of the low temperature brittleness phenomenon that occurs in both the tensile and impact tests. It was decided to study as pure an iron as possible and to use the tensile test in order to simplify the problem as much as possible. Two series of iron were used throughout the investigation: iron A, obtained from the National Research Corp. and supplied as gas-free, high purity iron; and iron B, obtained from Fast' and produced by melting iron under purified hydrogen. Typical analyses of samples of both irons, after fabrication, are given in Table I. The main difference in composition of these irons is in their nickel and oxygen contents. Nickel has a very large solid solubility in iron. However, oxygen has an extremely small solid solubility. An attempt was made to reduce the oxygen content still further by remelting under purified hydrogen. This was successful in reducing the oxygen content to -0.0006 pct. However, no results on tests of this iron are included, since difficulty was encountered in fabricating the ingot. Wire specimens 1 mm in diameter were used for the investigation. The wires were produced from the ingots, as supplied, by cold rolling and swaging, with intermediate vacuum anneals at 700°C. Care was taken to reduce preferred orientation in the wires to a minimum by keeping the percentage of reduction in area between anneals of 30 to 40 pct. X-ray transmission photographs showed no indication of preferred orientation. The final grain size of iron A was 20 to 24 grains per linear mm and of iron B, 16 to 18 grains per linear mm. All specimens were tested in the decarburized and denitrided condition unless otherwise stated. The procedure was to pass hydrogen, saturated with water vapor at 26oC, over the specimens at 730°C for 2 hr. The specimens were quenched in iced water and then annealed in a vacuum of - 5x10-6 mm Hg for one day at 560°C to remove hydrogen. Higher temperatures were used for the vacuum anneal but this temperature was found to be quite satisfactory in removing hydrogen. The specimens were slow-cooled after the vacuum anneal. Where it is stated that the specimens were carburized, the specimens were given an identical decarburizing treatment and then carburized by passing hydrogen, saturated with pure n-heptane vapor at 0°C, over the specimens at 730°C. The specimens were then homogenized at 730°C for 2 hr in dry hydrogen. After the carburizing treatment the specimens were given the same vacuum anneal as for the decarburized specimens. The carbon content was determined from the maximum value of the internal friction carbon peak.2 Apparatus Fig. 1 shows a diagram of the tensile apparatus, with half the cooling coil removed. The cooling coil enabled temperatures from 200" to 77.2oK to be obtained. The apparatus was designed to fit a standard Tinius Olsen Universal tensile machine. The apparatus consisted of the rigid plate A which carried two carefully machined hooks H. These hooks attached the plate firmly to the moving crosshead of the tensile machine. The lower grip B was rigidly suspended from the plate A by three stainless steel rods. The upper grip C was joined to the upper grip of the tensile machine by the stainless steel rod E. The lower part of the apparatus was surrounded by a Dewar vessel, which was made a sliding fit inside the brass collar D. The specimen was held in a clamp which fitted into the grip, forming a ball and socket joint (see inset a). This was to attain as nearly pure

Jan 1, 1954

By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

Experimental work on the properties of high-purity alloys of the copper-man-ganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. Previous Work Heuslerl conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilib- rium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alpha-beta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350' to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur6 have also noted this precipitate. Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By George Burrell

INTRODUCTION THE senior author of this paper, while in Colorado on other official business, made a trip to the Cripple Creek gold-mining district to get more data than are at present available regarding the composition of the gas that issues from the rock into the mines of the district. This was done at the suggestion of George S. Rice, Chief Mining Engineer of the Bureau of Mines. There are many questions of interest and importance in connection with the ventilation of the mines in the Cripple Creek district, such as the menace to life and mining of a suffocating gas entering the mines from the rock, the danger due to powder smoke (from blasting operations), and danger of continued inhalation of rock dust by the miners. This report confines itself to the first problem, the gas from the rock, and principally to one phase of this question, the composition of the gas and its effects on men and lights. A more thorough study of this and other ventilation problems is planned. That the, rock gas is a real menace is shown by the fact that miners (variously estimated from 25 to 50 by different persons interviewed) have been killed by it in the 25 years that mining has been vigorously carried on at Cripple Creek. Many men have had narrow escapes from death, some of them having been incapacitated for days. In addition, much loss of time results because at certain periods of the year or on certain days it is impossible to enter some workings. At a few mines fans force air into the workings, thus supplementing the natural ventila-

Jan 5, 1916

Jan 1, 1952

By R. H. Hadfield

Professor ArnolD, of the Sheffield Technical School, who has done so much excellent work in metallurgical research, recently produced, with the aid of aluminum, a sound ingot and bar from the purest known Swedish brand containing 99.8 per cent. of pure iron. Table 1. shows the physical quantities of this metal. TABLE I.— Tests of a Sample of Almost Pure Iron Prepared by Professor Arnold from D. v Ewedish Bar, Containing Before Fusion 0.04 Per Cent. of Carbon. I. II.+ III. Series mark,.. 136 1.371F ...... C, 0.07 0.07 Si, 0.04 0.04 8, 0.02 0.03 ...... Analysis, per cent,. .. P, 0.02 0.015 ...... Mn, 0.06 0.07 Al, 003 ............ Fe, 99.76 99.81 ...... Specific gravity,........... 7.863 ...... Original diameter, inches,. .. 0.564 0.798 0.798 Original area, square inches,. . 0.25 0.50 0.50 Limit of elasticity, tons per square inch,...... 18. 3.8 Breaking-load, tons per square inch,. 21. 23. 14.75 Total elongation, per cent., measured on 2 in.,...... 50. 49.25 61. Total reduction of area, per cent.,. 80. 69.60 61.20 Extension at permanent set, per cent.,...... 0.007 ...... silky and Appearance of fracture,. .. . silky i granular in parts.

Jan 1, 1894

By Samuel Hoyt

THE writer has long been interested in seeking an explanation of the upper heat effect in the copper-tin alloys over the a + ß range, first described in 1913. These notes are offered, not at all as the final explanation of this heat effect, but rather to indicate certain progress which has been made toward establishing what happens over this temperature interval. While working on the thermal analysis of the copper-rich kalchoids (copper-tin-zinc alloys), it was noted that those alloys containing major portions of tin and minor portions of zinc exhibited two marked heat effects, one at about 520° C. and the other at about 600° C., instead of the single effect which is generally observed in either of the two binary series. This matter was discussed with Dr. Guertler, who suggested that a heat effect at about 600° C. in the pure copper-tin alloys might be expected. This led to a more searching examination of the thermal critical points in the pure copper-tin alloys, with the result that a marked, although somewhat weak, heat effect was located at about 600°. Somewhat later, this upper heat effect was discussed with Dr. Burgess, and it was requested that the Bureau of Standards make heating and cooling curves of one of these alloys for the purpose of removing any possible doubt as to the actual presence of the heat effect. Results obtained by the Bureau are given in Plate I. In an earlier paper1 differential curves were published showing that the heat effect occurred at constant temperature over the a + ß range and increased in magnitude with the amount of a up to a point somewhat above 20 per cent. tin. No heat effect was noticed at this temperature in the eutectoid alloy. The existence of this heat effect seems to require a modification of the present copper-tin diagram in the a + ß field, and it has been the object of the work here presented to secure the evidence upon which such a change should be based.

Jan 12, 1918

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By L. W. Legerwood

During the past three decades, the oil industry has expended increasing eflorts seeking improved drilling tools or systems to reduce drilling costs. The total cost of these efforts is unknown, but it certainly amounts 10 tens of millions of dollars. Most of the "new" system that past and present investigators have sought to develop actually are old public information. In seeking to implement new-systern concepts, investigators have tested the following: impact at frequencies ranging from 6 to 300 cycles per second; electrical, mechanical and hydraulic meam of actuating percussors; bit rotary speeds up to 2,000 rpm; electric and hydraulic bottom-hole means of rotating bits; bottom-hole machines with power outputs up to 400 hp; shock waves; explosives; high-velocity pellets; flame; arc; grinding wheels; abrasive jets; erosion by high-velocity gases; chemical attack; electric current; magnetic waves; retractable rock bits; reelable drill pipe; continuous coring with reverse circulation; and automation of drilling rigs. Table I shows how these investigations are grouped for discussion purposes in this paper. In spite of these efforts to discover new and improved systems, rotary drilling main;aim its economic leadership. Undoubtedly, rotary drilling costs will continue to be reduced by rigid application of the best available technology and by development of new rotary technology. In view of the extensive past development programs, however, significant long-range improvement appears to be a research, not a development problem. Research must postulate and prove theories and principles governing variour subsurface rock-failure processes pertinent to both rotary and new systems. Ah, research must produce physical and engineering data relative to these processes. When such information is available, earth boring will graduate from an art to a science. Major improvements in rotary drilling can then be expected, and the systematic evolution of an improved drilling method can be initiated—with a strong probability for success. Development of drilling methods other than rotary drilling has been one approach investigated by the industry as a means for reducing drilling costs. Major cost-reduction efforts, however, have been centered on engineering development work aimed at incremental improvements in rotary drilling. A relatively minor effort has been expended to establish basic physical principles and engineering data pertaining to the earth-boring process which can serve as a foundation for the development of cost-cutting drilling hardware. Current oil-industry economic trends have added impetus to the need for effective programs to reduce drilling costs. However, areas for expanded future efforts should be selected only after careful study of past investigations. It is the purpose of this paper to review past and Dresent industry efforts to develop new drilling tools or systems and to suggest areas where additional science is needed. Past reviews of drilling methods have been limited to a few processes prominent at the time the reviews were made. This paper seeks to present a concise, well organized review of all methods that have received actual development or test work. The preparation of a paper seeking to review all past developments is fraught with many difficulties, not the least of which are errors in or obsolesence of printed matter used as source material and the lack of data on industry developments which have not been published. Since de-

By J. Chipman, N. J. Grant, H. L. Bishop

Lime and dicalcium-silicate crucibles were equilibrated with molten iron and liquid slags containing iron oxide and small amounts of sulfur. The oxygen content of metal, iron oxide activities, and desulfurization values of the slags were determined in the temperature range 1530 to 1700°C. The influence of magnesia in the slag and the temperature dependence of the solubility of lime in liquid iron oxide and the ferric oxide content were established. The temperature contour of the liquidus surface of iron-silicate slags saturated with lime and dicalcium silicate was also established at 1600°C. THE importance of the role that slag composition plays in the refining of steel has been known for many years. Numerous studies have been made using actual plant data in order to establish the relationship between the composition of the slag and metal during the refining of a heat of liquid steel. These results rarely represent equilibrium conditions since completion of the various chemical reactions involved in steelmaking is seldom realized. In order to establish quantitatively the equilibrium conditions existing between the slag and metal, several laboratory studies have been conducted in the past 20 years to determine the reactions important in slag control. These investigations have included studies of simple liquid basic and acid slags as well as more complex slag systems which approach those commonly found during the refining of a heat of steel. Since most of the previous studies of simple basic iron-oxide slags equilibriated with molten iron were made in magnesia crucibles, it was not possible to establish the distribution of sulfur and oxygen between molten iron and slags consisting only of the three essential components, lime, silica, and iron oxide. This investigation was undertaken to establish the equilibrium conditions for simple lime-iron oxide and lime-silica-iron oxide slags. Accordingly, it was expedient to prepare crucibles both of lime and dicalcium silicate to establish the equilibrium conditions between molten iron and iron-oxide slags saturated with the refractory materials and free from other components. The only other studies of the equilibrium between molten iron and lime-saturated slags are those of Fischer and vom Ende, 1, 2 in which the solubility of oxygen was determined in an air atmosphere. The

Jan 1, 1959

By Sherwin Kelly

IN presenting this brief historical perspective, it is not my purpose to address myself to the geophysicists, to most of whom the story is already well known. My objective is to draw the attention of those who hold the belief that geophysics is something new, typically twentieth century, to the fact that fundamentally, whether it was known by the name of geo-physics or not, the science is an ancient and an honorable one. It began many centuries ago, and our modern civilization and its commerce owe a great debt to its founders, who today are likely to he overlooked and their names forgotten. The word "geophysics" means the physics of the earth, and is descriptive of a science that in many ways bears the same relationship to geology that astrophysics does to astronomy. When dealing with dis-tant stars or deeply buried rocks, the experimenter cannot reach them to obtain samples, which can be taken to his laboratory for study. He therefore exhibits the resourcefulness of Mahomet in the mountain episode, and makes the terrestrial globe or the cosmic universe his labora-tory, studying the effects of distant bodies on certain "fields of force"" which come to him across interstellar space, or through the rocks that make our earth. The application of these techniques of the physics laboratory to the study of the stars is the science of astrophysics, and to the investigation of the earth is geophysics. Yet the origin of the most valuable contribution to the world's trade and commerce ever made by geophysics remains lost in deep obscurity. Unknown even is the country wherein lived the unsung genius who invented the first geophysical instrument, the mariner's compass! Worse yet, it is not certain whether this invaluable guide of man had its begin-nings in Europe or in Asia. A Chinese legend tells of the Emperor Hwang-ti, who attacked his enemy Tchi-yeou on the plains of Tchou-lou in the year 2634 B.C., whereupon the latter magically raised such a fog that the Emperor could not pursue the retreating troops. Not to be outdone, the mighty ruler constructed a chariot that indicated the cardi-

Jan 1, 1938