Search Documents

By Franklin H. Sharp, Kenneth L. Clifford

During the last few years the New Lead Belt of Southeastern Missouri has become the main source of lead in the United States. It also produces significant amounts of zinc, copper and silver. The mines are located on a narrow, mineralized trend extending southward from Viburnum, MG. for about 35 miles. The ore occurs as replacement deposits in the Bonneterre lime- stone formation which is about 1000 ft below the surface. In most of the mines, enough water is produced to supply the milling requirements without any reuse. There are dry areas, however, and at least two mills must rely on water reclaimed from their tailings lake to augment the mine water. These mills have no choice but to utilize recycled mill water.

Jan 7, 1973

By G. A. Vissac

MOISTURE in coal must be considered as an impurity, just the same as ash, from the standpoint of utilization of the coal. Being incombustible, it reduces directly the heating value of the coal, and in addition absorbs heat for its evaporation. Its presence means useless expenditures in handling and transportation. In coke plants, extra moisture reduces capacity and may cause damage to brick work and equipment. Accordingly, the removal of extra moisture can be considered just as important as the removal of other impurities, such as ashes, in the modern coal preparation plant. Moisture, which can be removed by heating the coal up to a temperature of 100°C, may be retained in various forms: 1. As a film, on the surface of each coal particle, and in the interstices between particles, retained by capillary forces. 2. Or "occluded" inside the coal particles. This occluded moisture may be either free moisture (as in a sponge), or hygroscopic moisture which varies with atmospheric conditions, (also called "regain").

Jan 1, 1949

By Robert Mehl

THE purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2° C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsen1 that variations as great as 30° C. exist in the reported data on the A3 temperatures in iron-carbon alloys. For-tunately, the A3 temperature in pure iron is now known to be 910° C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato' on both hypoeutectoid and hyper-eutectoid steels.

Jan 1, 1937

Jan 1, 1901

By Robert F. Brindisi

There are approximately thirty to forty operating mills in the United States which are currently producing uranium yellow cake. This figure includes a significant number of in situ and by-product operations however the conventional acid leach flowsheet depicted in Figure 1 is the most common process used by domes- tic yellow cake producers. Ground ore is leached with sulphuric acid and the solids are separated from the pregnant liquor and washed in a series of counter- current decantation thickeners. After clarification of the pregnant liquor, uranium is recovered from the solvent extraction/stripping circuit by the addition of ammonia with precipitation of ammonium diuranate, or simply yellow cake. The yellow cake precipitate is then thickened in a conventional thickener before re- porting to the dewatering/washing unit operation. De- watered solids subsequently report to thermal drying, and clarified liquor from the dewatering/washing step is recycled to the yellow cake thickener. The yellow cake dewatering/washing unit operation is generally accomplished using either a solid bowl centrifuge or a rotary vacuum drum filter. In most cases the underflow from the yellow cake thickener is pumped to the dewatering/washing unit operation at approximately fifteen to twenty percent solids. For the purpose of this discussion ammonium diuranate, the product of ammonia precipitation from a conventional acid-leach uranium mill flow sheet, as discussed earlier, will be considered. With only slight adjustment this discussion will be equally applicable to sodium diuranate or uranium perioxide precipitates and to either in situ or by-product operations where such precipitates are generated. Some of the domestic uranium mills which have selected solid bowl centrifuges instead of vacuum drum filters for the dewatering/washing unit operations are listed in Figure 2. Why have these uranium mills, as well as others not listed, chosen to use the solid bowl centrifuge for this particular application? It is simply a matter of performance, reliability and economics. In the remainder of this paper the performance, initial cost, installation cost, maintenance and power consumption of both the solid bowl centrifuge and the rotary vacuum drum filter will be com- pared. In order to provide a consistent basis for comparison the appropriate sized (centrifuge or filter) unit for the dewatering/washing of 400 to 500 pounds per hour of yellow cake solids will be considered. Such a flow will usually be generated by a typical 3,000 ton per day (acid-leach) uranium mill.

Jan 1, 1980

By R. F. Burdyn

The inadequate use of centrifugation to economically recover solids from weighted drilling fluids reflects the need for better equipment and techniques for this putpose. Laboratory studies in the development of an improved separator are described in which an operating equation is derived and tested. Results show that the concentric cylinder geometry employed effectively separates bnrite from a suspension and that the operating equation provides a good approxinmtion for scale-up. INTRODUCTION Our current drilling technology frequently requires a high-density drilling fluid obtained by addition of barite. In the course of drilling, formation solids which are too fine to be removed either by screening or settling become suspended in the drilling fluid and gradually the volume of solids in the mud increases. The volume fraction of solids must be limited (if a satisfactory set of rheological parameters are to be maintained). A centrifugal separatorprovidesan economical way of accomplishing this. The barite recovery process can be considered as a separation of two solids. One, the light solids, composed of formation and added solids, has a specific gravity of 2.6 to 2.7; the other, barite, has a specific gravity of 4.2 to 4.3. This density difference, plus the fact that the average light-solids particle size is much smaller than the average barite particle size, permits separation by a centrifuge. In drilling fluids some of the coarse particles of the light-solids-range will settle faster than fine particles of the barite-particle range. As a result a complete separation of the two species is not possible. since the object of the process is not merely recovering the maximum amount of barite but includes as well removing the maximum amount of light solids, an optimum barite recovery efficiency exists. From a practical standpoint this optimum cannot be determined in the field for each drilling fluid system, and in practice the separation is less than optimum, with some sacrifice of barite. Drilling technology has included centrifugal separators for barite recovery for more than a decade. Results have been reported by a number of investigators indicating that the process is practical and economica1. l-4 The decision to use a centrifuge is based on economics in which direct cost savings and the indirect benefits in rig time derived from improvement of the drilling fluid are important factors. One would expect that centrifugal separation of barite from drilling fluids would significantly affect barite consumption; however, this is not the case. The Minerals Yearbook shows an annual domestic barite consumption in the drilling industry of nearly 1 million tons.5 By rough estimate there are perhaps 80 separators presently in field use. Assuming half of these in use at any one time, operating an average of four hours per day, at recovery rates averaging 3,000 Ib of barite per hour, total annual recovery is about 90,000 tons. This is less than 10 per cent of he total barite used. I conservatively estimate that barite consumption in drilling operations can be reduced by 30 per cent through greater utilization of centrifugal separators. To encourage more widespread acceptance of centrifugal separators in the drilling industry, improved equipment and techniques would be very desirable. The present paper, covering theory and results obtained from a laboratory model, is the first in a series on he development of an improved mud separator for field use. THE CONCENTRIC CYLINDER GEOMETRY AS A SEPARATING DEVICE Consider the geometry shown in Fig. 1, consisting of two concentric cylinders separated by an annular space. These are arranged so that the outer cylinder is fixed and the inner one can be rotated about its axis on shafts sealed against the ends of the outer cylinder. If the outer cylinder is fitted with openings at either end, the inner

Jan 1, 1966

By E. J. Duggan

CLIMAX ore is an altered and highly silicified granite, about half of the gangue being quartz. Molybdenite is the only mineral recovered and most of it is intimately associated with the quartz in fine veinlets. Other minerals are molybdite, pyrite, and chalcopyrite. Although the molybdite may be readily extracted by hydrometallurgical methods, its content is too low to make this profitable. The pyrite ranges from 2 to 5 per cent and the chalcopyrite from 0.03 to 0.05 per cent. There is not enough copper to make its recovery attractive and one of the problems is its elimination, and that of pyrite iron, from the final product. On account of the high degree of dissemination of the molybdenite and the necessity of eliminating the iron and copper, fine-grinding followed by flotation is the only known feasible method of concentration. Two factors, peculiar to Climax ore, have a predominating influence on the metallurgical attack: (1) Molybdenite is one of the most easily floated minerals. High recoveries may be made with pine oil alone if the

Jan 1, 1946

By Richard J. Robbins

Mechanical moles have developed through a tedious process of evolution. At times it has seemed that tunnel borers have been subject to the same Darwinian rules of evolution as their zoological namesakes who, despite their efficiency, are highly specialized and still restricted to soft soil conditions near the surface of the ground. HISTORICAL HIGHLIGHTS The Robbins Co. began its work in this field in 1947 with the development of a twin-bore continuous coal miner. Although these machines were used primarily in coal, two of the early prototypes were used to bore tunnels through shale. Disk cutters were first used on these machines and showed promising results as core breakers between drag-bit kerfs. In 1953, James S. Robbins and Assocs. undertook the development of a 25-ft 9-in.-diam circular tunnel borer for Mittry Construction Co. to be used at Oahe Dam in South Dakota (Fig. 1). This is believed to be the first rock tunnel-boring machine built since the end of the 19th century when short sections of the Channel tunnel were successfully bored in chalk from both the English and French shores. Another Oahe Dam machine was built in 1955, and then a series of three small-diameter machines for the company's first real experience with medium-hard and hard rock (Fig. 2) None of these three could be considered a success, although they laid the groundwork for the success that followed. Interbedded shale and limestone in Pittsburgh and hard limestone in Chicago quickly pointed up the weaknesses in these machines which were used by Perini, Dravo, and Healey. Among the problems were the high breakage rate of tungsten-carbide drag bits, too much flexibility in the drive shafts, failure of high-pressure hydraulic systems, chain-conveyor failure, and general lack of rigidity and strength. In 1956 another attempt at medium-hard and hard rock-boring proved this time to be a success and a significant turning point in the development

Jan 1, 1970

AN intermetallic compound, Ni3A1, has an ordered fcc structure of type Ll2, and shows peculiar dependence of the yield stress upon temperature; i.e., the yield stress increases by a factor of six upon raising the temperature from 77" to 900K1, 2 This compound is technologically important, since many nickel-base superalloys owe their high-temperature strength to the peculiar yield stress behavior of Ni3Al. The only study of the elastic behavior of this compound was made by Davies and Stoloff,1 who determined Young's modulus of poly crystalline Ni3A1 between 300" and 730°K. The determination of single-crystal elastic constants of Ni3A1 is therefore of interest in connection with dislocation dynamics and is reported in this paper. A single-crystal specimen, 1 by 1 by 3 cm, was cut from an ingot generously supplied by Dr. B. H. Kear of Pratt & Whitney Aircraft. Following initial machining with a Servomet and a surface grinder, the specimen was etched and annealed at 1100°C for 5 hr in vacuum followed by furnace cooling. Two parallel faces were oriented normal to within ±l deg of a [I101 crystallographic axis by the back-reflection Laue technique. The parallel faces were hand-lapped, etched, and polished by the usual metallographic procedures. Final thickness along the [I101 axis was (0.9325 * 0.0005) cm. Chemical analysis gave an average composition of 87.35 pct Ni. Total impurity content is esimated to be no more than 0.1 pct. The elastic constants were calculated from measurements of ultrasonic waves which were propagated along the [110] axis. A longitudinal wave and two shear waves whose displacements are aligned along the [ 110], [li~], and [001] directions, respectively, are necessary in order to completely specify the three elastic constants. Two 3/6-in. quartz transducers were bonded to the parallel faces of the sample with ~ac-seal.3 Although this bond was sensitive to thermal shock, it performed satisfactorily over the entire temperature range for both longitudinal and shear wave propagation. A frequency of 5 mHz was employed in the method of Williams and Lamb4 in order to measure the absolute value of the ultrasonic velocity. The pulse-overlap technique of Mcskimin5 was also used at this frequency in order to determine the shift in the ultrasonic velocity

Jan 1, 1970

By Goodman, Richard E.

A complete rational analysis for design of excavation slopes and loaded rock masses is a desirable but perhaps unattainable goal. Irregular external and internal boundary conditions, poor understanding of failure criteria for large masses of rock, capricious material properties, and the importance of indeterminate forces and inaccessible and virtually un- sampleable rock defects emphasize the importance of experience in this aspect of rock engineering. The experience must be correlated with geological factors. In certain regions the accumulation of such experience through the observation of existing rock slopes in various formations constitutes an important aspect of studies for design of rock excavations.

Jan 1, 1969

By J. W. Fredrickson

VERY little information is available in the literature concerning the solubility of magnesium in titanium. Aust and Pidgeon&apos; report the solubility of titanium in magnesium to be 0.0025 pct at 650°C and 0.015 pct at 850°C. X-ray diffraction studies failed to detect any evidence of solid solubility. Based on the fact that the addition of titanium to magnesium increases the c/a ratio of magnesium, Busk&apos; suggested that the Mg-Ti system, like the Mg-Zr, is a peritectic. Eisenreich- eported the solubility of titanium in magnesium to be 0.003 pct at 655°C and 0.064 pct at 760°C. Removal of hydrogen from the melt increased the solubility of titanium to 0.115 pct at 800°C. Eisenreich proposes a peritectic-type diagram for the high magnesium side of the system. Recent work&apos; with Ti-Mg diffusion couples indicate that the solid solubility of titanium in magnesium is extremely small and that there is limited solid solubility of magnesium in titanium. Experimental work on the Ti-Mg system is complicated by the fact that the boiling point of magnesium is considerably below the melting point of titanium. Consequently, the usual alloying methods are impractical. Alloying was accomplished in this investigation by sheath-rolling compressed compacts." The alloys were made from titanium sponge and high purity magnesium. Chemical analysis of the sponge showed 0.04 pct Mg, <0.005 pct Al, <0.001 pct Cu, 0.05 pct Fe, 0.022 pct Mn, <0.0025 pct Ni, 0.007 pct Si, <0.005 pct V, and <0.01 pct Zn. All heat treating was conducted in a protective atmosphere by encapsulating the specimens in fused silica ampules under a partial pressure of helium. Equilibrium was achieved by holding the specimens at temperature for periods of 24 to 120 hr. The alloys were hot rolled, cold rolled, and annealed prior to solution heat treatment. Fig. 1 shows the constitutional diagram obtained for the Ti-Mg system up to 1.5 pct Mg. Oxygen was known to be present in the alloys; therefore, it is necessary to consider the alloys as ternary rather than binary and the diagram should be viewed as a plot of a section through the Ti-Mg-0 system. Other investigatorso have shown that the addition of oxy- gen to titanium stabilizes the a phase. The data presented in Fig. 1 indicate that the addition of magnesium to titanium tends to stabilize the p phase. Armour Research Foundation7 has shown that the addition of magnesium to zirconium lowers the a transus and is classified as a p stabilizer in that system. Magnesium is soluble in solid titanium to the extent of at least 1.5 pct in both the a and /3 phases. No intermetallic compounds or magnesium-rich phases were observed either by light microscopy or X-ray diffraction. However, this does not negate the possibility that such phases exist at higher alloy concentrations.

Jan 1, 1956

By Joklik, G. F.

Most publicity about the copper industry nowadays is focused on the adequacy of ore reserves and on excessive mining capacity. These concerns, stemming from public awareness of actual and potential shortages and oversupplies, relate to production rather than consumption. Perhaps the reason for this one-sided view is that copper is thought of as a commodity which is conspicuously traded in world markets, rather than as one of many industrial materials that serve today&apos;s rapidly changing technology. Copper differs from other widely traded commodities in that its real cost of production has progressively increased since World War 11. The reasons for the increase are identifiable by analyzing operations in one of the world&apos;s large producing centres, the copper province of Arizona. Another respect in which copper differs from some other commodities is that increases in demand occur less automatically in the case of copper than they tend to in commodities whose consumption is more directly related to population growth. The copper industry&apos;s current inability to generate and attract needed investment capital is attributable to these differences between copper and other commodities; it suggests that the concept of copper purely as a commodity is outdated. The key to the problem is better integration between the activities of copper producers and users. Depending on circumstances, integration takes various forms- for example, investment tied to long-term sales con- tracts between producers in developing countries and consumers overseas; common ownership of producing and manufacturing facilities in industrialized nations like the U.S.; and consumer-oriented research and marketing by the copper producers.

Jan 1, 1978

By Dudley L. Davis, E. C. Peterson

INTRODUCTION THE Darwin District is 30 miles east of Olancha which is 220 miles north from Los Angeles via U. S. Highway No. 6. The ore deposits occur in the Darwin hills that have been elevated above the Darwin Plateau by typical basin and range-type faults. Some of these faults have been active quite recently as shown by the displacement of Quaternary (?) basalt flows and the rejuvenation of erosion in Darwin wash. The ore bodies occur as fissure fillings and replacement of favorable beddings in a thick series of Paleozoic limestones, dolomites, shales and quartzites. Rich oxidized lead-silver ores were discovered in the early seventies. By 1875, Darwin had a population of about 5000, and by 1880 several small mills and smelters had been built. Early exhaustion of surface ores, the isolated location of the district, and fluctuation of metal prices caused intermittent operations until World War II. The district production is estimated at about $3,000,000 prior to 1900 and perhaps $4,000,000 between 1900 and 1945 when Anaconda purchased the major producing mines. For the past two years, daily production has averaged 75 tons of direct shipping and 150 tons of milling-grade ore. At present, 300 tons of mixed oxide and sulphide ore are treated by flotation, the oxidized lead minerals being activated by addition of sodium sulphide after galena and sphalerite have been recovered from the circuit. Extraction averages 85 pct of the lead, 80 pct of the silver, and about 33 pct of the zinc in a bulk concentrate. The mill is designed so that minor changes permit selective flotation of pyritic lead-zinc ores encountered at depth. GENERAL GEOLOGY The oldest rocks in the Darwin hills are a series of Paleozoic limestones, dolomites, shales and quartzites probably Pennsylvanian in age. These rocks have been intruded on the west by the Coso granite batholith and on the east by a granodiorite stock. Numerous sills and dikes grading from orthoclase granite to gabbro are exposed in the underground workings. The sedimentary rocks have been considerably folded and faulted, the most prominent structure being a northwest pitching anticlinal fold, the crest of which lies just west of the ridge line of the Darwin hills. The east limb of this fold has been intruded by the granodiorite stock and east of the stock the sediments show several closely spaced anticlines and synclines. The minor flexures on the west flank of the major fold are structurally important in localizing the ore in the Defiance and Essex mines of the Darwin group. There are three principal systems of faulting and fissuring, most of which are post-intrusive and premineral in age, with minor amounts of postmineral movement. The Darwin tear fault is the largest, most persistent fault in the district. It strikes N 60 to 95°W, dips steeply south and is traceable for about 1o miles. It is a normal

Jan 1, 1947

By H. D. Kessler, M. Hansen, R. J. Van Thyne

The phase diagram of the titanium-rich portion of the system Ti-Cr-Fe to 70 pct Ti was established by means of isothermal sections at 900°, 800°, 750°, 700°, 650°, 600°, and 550°C, using arc-cast alloys. An isotherm at 800°C was determined for the section bounded by Ti, TiFe2, and TiCr2. Micrographic analysis was employed as the principal method of investigation, supplemented by X-ray diffraction and incipient melting studies. A ternary eutectoid, ß ? a+ TiCr2 + TiFe, occurs at approximately 8 wt pct Cr, 13 wt pct Fe, and about 540°C. AMONG the first titanium-base alloys in commercial production were the Ti-Cr-Fe alloys. For this reason, the Materials Laboratory, Wright Air Development Center, sponsored an investigation of the system. No information on the constitution of the titanium-rich corner was available. Vogel and Wenderott studied titanium-poor ternary alloys.&apos; As part of this program, the binary systems Ti-Cr and Ti-Fe have been determined previously by the authors.&apos; Other investigators have also studied the binary systems Ti-Cr,3-7&apos; Ti-Fe.³,8-10 Both of the binary systems are characterized by the eutectoid decomposition of the ß phase. Most of the effort of the present work has been concentrated on the titanium-rich corner with compositions of less than 30 pct total chromium and iron content. The determination of isothermal sections was the experimental approach used to obtain the ternary phase diagram. Vertical sections were used to check the consistency of the isothermal sections. While this investigation was in progress, a study of the Ti-Mo-Cr system at Armour Research Foundation disclosed the existence of a high temperature modification of TiCr2 above 1300 °C.11 This allotrope has a hexagonal structure of the MgZn2 type, iso-morphous with TiFe2, whereas the low temperature modification of TiCr2 is cubic," of the MgCu2 type. The existence of allotropy in TiCr2 of course means a more complicated set of phase relationships in this general region than if the phase were monomorphic, as was first assumed. Additional studies were made late in the investigation in order to clarify the part that the hexagonal TiCr2 phase plays in the ternary phase relationships. These will be discussed in a separate section. Because they are of greatest practical significance, the phase relationships in the titanium-rich corner will be presented first, omitting the equilibria involving the hexagonal modification of TiCr2 in an effort to simplify the presentation somewhat. Experimental Procedure Materials: The titanium used in the preparation of the alloys was iodide crystal bar (99.9 pct pure) produced by the New Jersey Zinc Co. High purity chromium and iron were obtained from the National Research Corp. Table I gives the analyses of these materials. Melting Practice: Over 100 alloy ingots weighing 10 to 20 g were melted in a nonconsumable electrode arc-melting furnace. As the techniques are identical to those reported previously,12,13 they will not be detailed here. The ingots were melted in the cavity of a copper melting block insert under a slight positive pressure of helium. No measurable hardness

Jan 1, 1954

By Charles Albert Ashburner

The coal-fields of the United States have been variously classified as to their geographical positions. In 1887 I proposed slight changes to the classification generally used, for more convenient description of our coal-fields in my report on the statistical history of coal in the States during 1886 for the United States Geological Survey. This new classification seems to meet all practical requirements and has been generally adopted. The coal-areas are grouped in two divisions—the anthracite division and the bituminous division. The anthracite division, in a commercial sense, may be said to include the anthracite districts of Pennsylvania alone, although small amounts of anthracite are mined in Colorado and have been

Jan 1, 1890

By H. M. Woodroffe, H. K. Conn, S. J. Rice

World production of asbestos is estimated to be at a current level of almost 3.5 million tons, having more than doubled in the past ten years. A substantial part of the increase has been due to a rapid expansion in the Soviet Union. Production from that country during 1964 is estimated at 1.5 million tons and, as a consequence, Russia has displaced Canada as the leading world producer. Although traditionally the asbestos mining industry has been centered near Sverdlovsk in the Urals, two new producing areas have been under development for some time. It is expected that a new mine will be in operation in 1965 near Kiembi, Kazakhstan, some 300 miles south of Sverdlovsk, and an- other mine at Aktrovak in Tannu-Tuva, west of Lake Baikal. These developments will provide a significant increase in the production capability of Russia. Although internal consumption is expected to increase with the addition of new asbestos- cement producing facilities now under construction in Russia, there is some speculation that exports will also increase.

Jan 2, 1965

By Herbert K. Kutter

This paper is concerned with the physical phenomena in the fracture process of presplitting and only indirectly with the establishment of the optimum presplitting parameters. Its nature is therefore qualitative, rather than quantitative.

Jan 1, 1968

By V. Jares

DESPITE the fact that a combination of metals-aluminum-zinc-tin, and sometimes aluminium-zinc-cadmium-is extensively used for aluminum solders, as well as for die-castings, the constitution of these alloys has not yet been made clear. I. BINARY SYSTEMS The system aluminium-zinc is the basis of the ternary alloys under consideration. Their composition was made sufficiently clear by the investigations of Roscnhein and Archbutt,1 Bauer and Vogel,2 Sander .and Meissner,3 Hanson and Gayler4 and Isihara.5 Only the temperature of decomposition of the crystals s seems still to be doubtful, whether it is considered as a compound of Al2Zn3 (according to Bauer and Vogel) or as an intermediate phase of variant composition (according to Hanson and Gayler). This temperature is given by most of the authors, as in the neighborhood of 256° C., only Isihara giving 280° C. As its accurate determination is of special importance in the study of the ternary alloys under consideration it was experimentally controlled in the following manner: An alloy corresponding in composition to the formula Al2Zn3 was made, in which the temperature effect was found to be the greatest. This was drilled and a silver-constantan thermoelement inserted into the cavity so as to be in direct contact with the alloy. The whole was then very slowly heated and the heating and cooling curves determined. The transition temperature from the heating curve was found to be 281° C., whereas-from the cooling curve it was 252° C.

Jan 10, 1926

By M. E. Nicholson

IN order to understand how alloying elements influence hardenability through their effect on the rate of pearlite nucleation, it is advantageous to use a model to describe the mechanism of pearlite nucleation. The model which currently is most widely accepted has been described, among others, by Mehl et a1.1-3 and by Hultgren.4 Pearlite nucleation involves both the nucleation of ferrite and cementite.4,5 Cementite nucleates first, followed rapidly by the formation of ferrite at the cementite-austenite interface. The conclusion that cementite is the first phase to form during the process of pearlite nucleation is based, in part, on the observation that proeutectoid cementite is continuous with pearlitic cementite and that the orientation relationship between proeutectoid ferrite and austenite is not the same as that between pearlitic: ferrite and austenite.6,7 Recently, Smith" has suggested that the dissimilarity in orientation relations, instead of indicating the pearlite nucleation sequence, may be evidence that pearlite is nucleated in a grain adjacent to the one in which it is growing. Also, Modin9 as shown that ferrite in pearlite may be continuous with proeutectoid ferrite, and he has also shown that proeutectoid cementite is not always continuous with pearlitic cementite. Thus, it appears that the conclusion that cementite always initiates the pearlite nucleation process is open to serious question. The author believes that important evidence on the question of how pearlite is nucleated exists in the rates of pearlite nucleation of different steels. The following is a review and analysis of this evidence. If the nucleation of pearlite is considered as requiring the nucleation of both cementite and ferrite, then the time to nucleate pearlite consists of the time to nucleate the first phase to form, plus the time to nucleate the second phase at the advancing interface of the first. In the absence of a visible proeutectoid constituent, the second phase must be nucleated very soon after the first. If cementite is the first phase to form, the time to nucleate pearlite will be approximately equal to the time to nucleate cementite. Since the nucleation rate of a phase precipitating from solid solution increases with the degree of supersaturation, it would be expected that the rate of pearlite nucleation should increase with increasing carbon content. Digges10 has shown that the reverse is true. He determined the quenching velocity necessary to suppress pearlite formation in plain carbon steels as a function of carbon content. His results showed that pearlite formation could be suppressed with lower quenching velocities as the carbon content of the steel increased, at least up to 1.25 pct C, the highest carbon content he studied. Thus, it would appear that in plain carbon steels, in which pearlite is formed at the nose of the C-curve, the hypothesis that cementite nucleates first does not predict the observed change in nucleation rate. The validity of the current model of pearlite nucleation may be tested also by determining whether or not it predicts the relative influence of alloying elements on the nucleation of ferrite and pearlite. This can be done best by a consideration of the changes in a TTT diagram produced by a change in alloy content. Hultgren4 suggests that the general shape of a TTT diagram, as well as what constituents will form from austenite, can be predicted from the relative nucleation rates of ferrite and cementite. This is illustrated in the schematic diagram for a hypoeutectoid low alloy or plain carbon steel shown in Fig. 1. The C-curves for ferrite nucleation and for cementite nucleation are represented by AA&apos; and CC&apos;, respectively, and the start of ferrite formation and pearlite formation are represented by AX and BC respectively. Adopting the current theory, Hultgren suggests that between X and C pearlite forms directly from austenite, since cementite nucleates more rapidly than ferrite in this temperature range. Conversely, at temperatures above Tx, ferrite is the first to nucleate and proeutectoid ferrite is formed. As proeutectoid ferrite grows, austenite becomes enriched in carbon, so that the cementite nucleation rate is increased. As a result, pearlite nucleation above temperature Tx is accelerated, beginning along BX and not along C&apos;X. Temperature T, represents the temperature at which the nucleation rate of ferrite equals that of cementite. By extending this type of reasoning, using the principle that the nucleation rates of ferrite and cementite increase with increasing supersaturation of austenite with respect to these phases, it should be possible to predict the influence of carbon content on the shape of the isothermal transformation diagram. For a slightly higher carbon content than that of Fig. 1, the curve A A&apos; representing the beginning of ferrite formation should be moved to the right, whereas the curve CC&apos; representing the beginning of cementite formation should be moved to the left. For hypoeutectoid plain carbon and low alloy steels, this prediction does not agree with existing data. Instead, as the carbon content is increased, the pearlite curve moves to the right along with the ferrite curve and always appears to join it tangen-tially. This behavior is demonstrated by the TTT-curves of a series of manganese steels" shown in Fig. 2. In this figure, TTT-curves for four alloys containing 0.20, 0.40, 0.60, and 1.20 pct C are superimposed. The curves are identified in the figure legend. The letters F, P, and C are used to indicate the start of ferrite, pearlite, and cementite formation, respectively. In these steels, it appears that the nucleation of ferrite and of pearlite are related processes. As a result of the foregoing evidence, it is proposed that the formation of pearlite be considered as follows: Either ferrite or cementite may nucleate from austenite, then grow until the remaining phase is nucleated at the interface between the growing phase and austenite. (The growth of the first phase to form is assumed to be accompanied by a composition change in the adjoining austenite.) According to this model there are two modes of nucleating pearlite: 1—where cementite initiates the succession

Jan 1, 1955

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon&apos; and carbon&apos; on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of&apos; the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon&apos; and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953