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By Attilio Ligasacchi

The production of magnetite in copper smelting has been the subject of wide investigation in the past.1-9 It is accepted that most of the magnetite is produced in the converters and returned to the re-verberatory furnace with the converter slag. Part of this magnetite is circulated back to the converters in the matte. As a result, if proper fluxing practice is not followed, and temperatures in the converting process are not strictly controlled, an undesirable circulating load of magnetite may occur. This might ultimately lead to saturation in the reverberatory bath with consequent settling of the magnetite at the furnace bottom. This paper contains the cumulative results of a series of investigations on the formation and control of magnetite presently being conducted by the metallurgical department of the Chino Mines Division of Kennecott Copper Corp. THE METHOD USED FOR THE DETERMINATION OF MAGNETITE AND OTHER MAGNETIC MATERIALS Conventional wet chemical magnetite analyses are neither reproducible nor theoretically sound. These analyses are sensitive to time, temperature, and heating rate-all factors which tend to decrease their accuracy and reproducibility. To overcome the unreliability of the above method, H. W. Mossman1 developed an inductance bridge magnetite "meter" which completely replaces the wet chemical analysis with the advantage of quicker and reproducible results. Fig. 1 is a schematic diagram of the meter in use in the Chino metallurgical laboratory. When a pulverized specimen with magnetic properties is placed in coil A of the inductance bridge circuit, the permeability of the core is increased, causing a voltage drop across the coil. The unbalance is amplified to operate the balancing motor which adjusts the movable iron core in coils C and D to bring the bridge back to balance. An indicator arm connected to the movable iron core indicates directly the percent, or weight, of the magnetic material in the specimen. Coil B acts as a reference coil and a zero adjustment. The meter is standardized with a set of various amounts of -100 mesh pure magnetite crystals (99.8 pet Fe3O4) thoroughly mixed in a test tube with -100 mesh quartz sand. These mixtures are combined with inert transoptic powder and heated to 140° to 160°C (melting point of the powder) and subsequently cooled to room temperature, solidifying the whole mixture, in this manner eliminating any possible preferential orientation of the magnetite grains. In order to determine the effect of the particle size" of the magnetite and other magnetic materials on the meter determinations, five size fractions were obtained by wet screening of the 99.8 pet pure magnetite and several reverberatory matte and slag samples. The following size fractions were investigated: -80 + 100; -100 + 150; -150 + 180; -200 + 250; -250 + 300 and -100 mesh. The deviation of the meter readings for the various sizes of each sample never exceeded ±0.3 pet. This deviation is considered well within the accuracy needed for common smelter operation procedures. Further investigation proved also that grinding slag and matte samples in our laboratory disc grinder normally produced a powder constituted of 95 pet -200 + 300 mesh. For practical purposes a - 100 mesh size was used as standard for our studies. It was also found that for rapid determinations tamping of the sample in the test tube was sufficient and gave comparable results with those samples solidified with transoptic powder. For the purpose of this study we define the magnetite content in copper smelter slags and matte as the equilibrium amount of crystalline Fe3O4 existent in the specimen at a given reference temperature, excluding any secondary magnetite precipitated in the specimen during nonequilibrium conditions. MAGNETITE DETERMINATION IN SLAGS Since it is impossible to ascertain the status of equilibrium of a conventional slag sample, due to

Jan 1, 1965

By I. F. Jackson, H. L. Hartman

Hard-metal inserts have received considerable attention in the mining industry recently for a variety of excavating and penetrating purposes. Their use in percussive drilling and in coal cutting machines is well known, but attempts to utilize them in cutting materials such as dimension stone have been discouraging because of excessive tool wear and failure. Particular attention is given to those properties of hard-metal inserts that affect their resistance to wear. A consideration of the actual wear mechanism shows the importance of correct mounting of the inserts and of the selection of suitably powered driving motor so as to achieve minimum tool wear and maximum tool life. Comparisons are made between the performances of types of hard-metal inserts, relating their inherent properties with results obtained in laboratory tests. As part of a broad program to improve the quarrying and processing of industrial minerals, The Pennsylvania State University has been investigating the machinability of slate under laboratory and field conditions. It should be emphasized that the results of the research presented in this paper are also applicable to other natural structural materials, and particularly to the more workable ones such as limestone and sandstone. Improvements which accrue in cutting and sawing should prove of benefit to all the dimension stone industry. Further, it may be pointed out that the results reported here are applicable to rotary drilling (with drag bits) as well as to cutting and sawing of rock. INVESTIGATIONS IN RELATED FIELDS The investigation was initiated with an extensive survey of available literature related to metal cutting and to rotary drilling. The following similar features between metal cutting and slate cutting became evident: 1) Hard-metal inserts are widely used as a cutting tool in both cases. 2) The forces acting on the tool may be resolved into normal and tangential components. 3) Rate of penetration and tool wear are important criteria in each case. On the other hand, important differences also exist: 1) Most metals, exhibit plastic behavior, while slate (and most rock) is a brittle material under normal conditions. 2) In metal cutting the component of force acting parallel to the surface of the workpiece is considerably greater than the force holding the tool against the workpiece. 111 slate cutting, this situation is reversed. Similarities between drag-bit rotary drilling and slate cutting are as follows: 1) In both casts, a tool, usually of the hard-metal insert type, is used to penetrate a brittle material. 2) The drilling forces and related variables, such as rotation speed, are similar. 3) Chip formation in each case is essentially the same. 4) The shape of the tool is similar in rotary drilling and slate cutting. Important differences are also apparent: 1) The objective of drilling is to produce a directed hole, while in cutting it is to form a kerf. In core drilling, however, a kerf is also produced. 2) The horizonta1 component of force in rotary drilling decreases from the center to the outside of the tool, whereas in slate cutting the component is almost uniformly distributed across the width of the tool. 3) The power absorbed in the drill rod is greater in rotary drilling. 4) The clogging action of chips, if excessive power is applied to the tool and if flushing is insufficient, is more serious in rotary drilling. Because of the striking similarities between metal cutting and slate cutting, and between rotary drilling and slate cutting, it was considered that the findings of investigators in those fields would serve as a guide for experimental studies of slate cutting. The following is thus devoted to a discussion of those aspects of metal cutting and rotary drilling pertinent to the present investigations.

Jan 1, 1962

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland' found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.' determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-' torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.' These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren' and Miller' were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969

By F. Brons, V. E. Marting

In the past, other authors.1, 2 have studied the influence of a skin effect on the productivity of a well. This skin effect, expressed by the skin factor S, is considered to be caused by a thin layer of impaired permeability immediately around the wellbore and extending vertically over the whole productive interval penetrated by the well. The skin factor S is defined as follows. Based on this, the impairment in productivity caused by a skin can be expressed by the fractional loss in productivity I, which is the loss in productivity divided by the total unimpaired productivity. For compressible flow in a stabilized well which drains a circular area of radius re, 1 is given by The present paper deals with a different kind of productivity impairment. Consider a well in which part of the productive formation is blocked off completely, either by incomplete penetration or by exclusion of parts of the productive zone by blank casing. In Fig. 1 (A, B and C), three examples are shown. Fig. 1(A) shows the situation where a well only partially penetrates the formation. This often is done to combat the actual or imagined danger of bottom-water coning. Fig. 1(B) shows a well producing from only the central portion of a productive interval. This type of completion is sometimes used where both water and gas coning are a problem. Although the case of a well producing through perforated casing cannot be treated in a manner similar to the previous two cases (where radial flow in the horizontal plane is assumed), Fig. 1(C) shows several intervals open to production and qualitatively describes this case (as will be discussed later). To study the loss in productivity in all these cases, two parameters are introduced which fully determine the impairment. The first is the penetration ratio "b," i.e., the total interval open to fluid entry divided by the total thickness of the productive zone. The second is the ratio hlrw. In this ratio, rw is the wellbore radius. The definition of h is more cumbersome. In Fig. 1(A), h is the thickness of the total productive interval. The streamline configuration for this case of partial penetration is basic to the other two cases considered (Views B and C of Fig. 1). It will be obvious from Fig. i (A) that the flow lines in the uppermost portion of the formation will be essentially horizontal, while those in the lower portion will curve upward toward the well. In Fig. 1(B), with only the middle portion of the zone open to production, the streamline configuration. of the upper half will be an exact mirror image of that in the lower half of the zone. Hence, for the case illustrated in Fig. 1(B), h is defined as one-half the total sand thickness. It follows, then, that in Fig. 1(C) h is one-half the distance between corresponding points in adjacent intervals. (In gun-perforated casing, h would be one-half the distance between perforations.) In a paper by Nisle4 and a paper given by the present authors5, the mathematical theory was developed for the cases under consideration. In the present publication, the emphasis is put on the results of these studies; consequently, the equations derived in Refs. 4 and 5 will be omitted, for the most part. The pressure drop p in a well producing from only a portion of the total formation thickness can, in analogy with Eq. 1, be expressed by Numerical solution of Eq. 5 by use of the IBM 650 leads to the following important conclusions. First, during a short period after starting production (usually on the order of a few minutes), the function p(b) is given by

By Robert B. Hoy

If the reader finds that the basic information in a commodity chapter is insufficient, he can consult the appropriate sources in this chapter to find more detailed or more up-to-date information. In these days, technology develops so rapidly that this 5th edition will be somewhat out of date even by the time it is distributed. A comparison of this edition with the 4th edition (1975) of Industrial Minerals and Rocks will clearly demonstate how rapidly the scene changes. One of the best sources of new information, of course, is attendance at technical meetings. For example, the papers presented at the national and sectional meetings of AIME usually discuss new developments in the respective divisions of the society. Frequently this information is available in Preprints. In addition some are printed in Mining Engineering and/or the Transactions of the Society of Mining Engineers of AIME. Furthermore, other professional and trade journals contain articles pertinent to the field. A journal introduced in 1967, Industrial Minerals, published by the Metal Bulletin, Ltd., London, is an excellent source of information. The Mining Journal, Ltd., also in London, publishes a weekly journal, a Mining Magazine (monthly), and a Mining Annual Review. The latter covers the field from three aspects: (1) by commodities, (2) through technical developments, and (3) geographically. The Industrial Minerals Directory 1977, 1st ed., Metal Bulletin Books, Ltd., London, provides addresses of organizations in the field. Other useful magazines and periodicals include Engineering and Mining Journal, Pit and Quarry, Rock Products, and World Mining, all published in the United States. In addition many new books related to industrial minerals have been published since the 4th edition of Industrial Minerals and Rocks. Most of these are included in the bibliography of each chapter in this volume. Another excellent information source is the proceedings of the Forum on Geology of Industrial Minerals. This group, which held its 18th annual meeting in 1982, is sponsored by a state geological survey or another mineral agency on a rotational basis. The proceedings have been published by the various sponsors and are available as indicated in Table 1. Two major sources of basic industrial mineral and rock data in the United States, and also a good source for many foreign countries, are the US Geological Survey and the US Bureau of Mines. The two agencies publish many reports and maps on a variety of geological and mining subjects. In addition, each agency has an indexed list of all their publications with a free service announcing new publications: New Publications of the Geological Survey, US Geological Survey, 329 National Center, Reston, VA 22092 and New Publications-Bureau of Mines, Publications Distribution Branch, US Bureau of Mines, 4800 Forbes Ave., Pittsburgh, PA 15213. The US Bureau of Mines (USBM) publishes annually Minerals Yearbooks which provide statistical data on mineral products including production, consumption, imports and exports, as well as information on new developments. Another very useful USBM series is called Mineral Facts and Problems. Editions were published in 1960, 1965, 1970, and 1975. Four major series of publications by the Bureau are Information Circulars, Reports of Investigations, Mineral Trade Notes, and Minerals and Materials. The last two are particularly good for news of foreign developments. The Bureau of Mines Employee Directory, available at all USBM offices, lists addresses and telephone numbers for all offices as well as same for all commodity and area specialists.

Jan 1, 1983

By C. R. Claus, G. A. Standish

Since March. 1945, the Magnolia Petroleum CO. has drilled 39 wells in Southwest Coastal Louisiana. All wells were drilled within a comparatively small radius, but the area provides a large variety of problems. The deepest well drilled was 13,518 ft, and the total depth averaged 10,977 ft. Throughout this period drilling mud control and types of mud handled were: (I) phosphate, (2) red lime (late conversion), (3) red lime starch (early conversion), (4) red lime starch oil emulsion, (5) precision controlled low alkalinity-low lime content. and (6) gel muds for completion purposes. Improvement has been obtained in effecting some or all of the following: (I) more rapid penetration, (2) reduction in drilling hazards, (3) better evaluation of cores and logs, and (4) better completions. The geological sequence of zones penetrated range from recent sediments at the grass roots through the Frio section. Anticipation of high-pressure zones and incompetent formations entails precision control of drilling mud weights, and the unconsolidated nature of the various zones requires constant attention to the filtrate, viscosity, and gel strength values. In the Chalkley field, particularly, this combination of problems exists, where the formation pressures and overburden weight density values are in very close proximity. Design of casing and drilling mud programs must be modified to fit each well. INTRODUCTION Field and research work on drilling fluids has made constant progress, enabling operators to prospect progressively deeper horizons. Numerous papers have been written on the theoretical aspects of drilling fluid devel- opment, but in the field engineers have found it difficult to evaluate the role of specific mud constitutents when dealing in terms of thousand barrel mud systems. For that reason field data is somewhat lagging in technical report writing. However, applications of new techniques in the field have usually paralleled, and in numerous instances preceded, research work. The information obtained by Magnolia Petroleum Co. in the course of drilling 39 wells within a comparatively small area in Southwest Coastal Louisiana provides an excellent opportunity of reviewing a specific example of drilling mud evolution. A large variety of problems has been coped with, the most important result being that every well was successfully drilled to its projected total depth. The discussion begins with the advent of deep drilling in this area in March, 1945, and is concluded with a resume of recent drilling operations in the Chalkley field. The primary purpose of this paper is to describe the evolution in types of drilling fluids as it occurred and its application in the solution of various drilling problems. All of this information and experience resulted in the successful drilling of the three wells in the Chalkley field, where a combination of the most sound techniques was necessary in carrying drilling operations to the projected total depths. Other operators along with service company engineers have contributed considerably through the interchange of ideas and information to this paper, but the data and conclusions which are contained are based on first-hand observation of Magnolia Petroleum Company's drilling operations. The 39 wells drilled by Magnolia Petroleum Co. average in depth 10,977 ft per well, while the maximum depth penetrated was 13,518 ft. The cost of drilling fluids have varied from $8,700 to $165,000, with the over-all drilling costs ranging from $74,000 to $543,000 per well. This wide variance illustrates the unpredictable nature of each well and the effects on over-all cost when high density muds are required to control

Jan 1, 1955

By O. N. Carlson, K. E. Solie

The brittle-ductile transition temperatures of single and poly crystalline chromium metal were studied as a function of nitrogen concentration and chromium nitride distribution. It was observed that In recent years there has been an increasing interest in chromium-base alloys for high-temperature applications. The principal disadvantages, however, have been the difficulties of fabrication and the design problems associated with a material of such limited ductility. Various studies have been the effects noted in the poly crystalline material are essentially reversed in the single crystals. These observations are discussed in terms of existing theories for the brittleness of chromium. conducted recently directed toward a determination of the cause of this brittleness and to find ways for minimizing its effects. Allen et al.,' Wain Abrahamson and rant,' and weaver4 have carried out studies on the effects of interstitial impurities on the brittle-ductile transition of chromium metal of various degrees of purity. These investigations have shown that oxygen has little or no effect on the transition temperature of chromium in all conditions studied but that carbon increases the transition temperature under all conditions tested. Nitrogen was found to increase the transition temperature in the wrought condition and in the quenched or cast conditionS but reportedly has no effect in the furnace-cooled condition.

Jan 1, 1964

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman' have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By H. E. Powell, A. A. Cochran, R. E. Coleman

Infrared spectroscopy, employing the internal reflection method in conjunction with solvent extraction techniques, was used to study surface reactions between aqueous potassium ethyl xanthate and both sphalerite and precipitated zinc sulfide, each activated with aqueous copper sulfate. It was determined that reactions occurring on the sphalerite and zinc sulfide surfaces produce the reaction products ethyl dixanthogen and cuprous ethyl xanthate, some of which are adsorbed on the mineral surfaces. As the pH of the xanthate solution increased from 5.6 to 11.0, the amount of cuprous ethyl xanthate on powdered sphalerite surfaces decreased and the amount of ethyl dixanthogen first increased and then decreased. It is generally accepted that the collector potassium ethyl xanthate will not float the mineral sphalerite (ZnS). However, Gaudin1 showed that sphalerite readily floats if activated with certain metal cations before exposure to the xanthate. Copper sulfate (CuSO4) was found to be the best activator for sphalerite. The over-all flotation reagent reaction, as given by Gaudin,3 is as follows: While this is the over-all reaction, the exact mechanism of the reaction and the intermediate compounds that may be formed are not yet known with certainty. Important work has been done in Russia by Plaksin

Jan 1, 1968

By R. D. Vaughn

The analysis of laminar flow of power-law non-Newtonian fluids in narrow, eccentric annuli is employed in this paper to discuss the problems of lubricant flow in journa! bearings and of errors introduced by eccentricity in experimental studies with concentric annuli on extruders and wellbore annuli. The velocity profile and pressure loss-flow rate equations are developed for the laminar flow region. In addition, the expected error in flow rate and pressure-loss measurements for concentric annuli as a result of eccentricity is determined. For example, a 10 per cent displacement of the core of an almost concentric annul us would cause a 1.8 per cent decrease in the observed pressure loss for a fluid with a power-law exponent n of 0.25. The corresponding increase in the observed volumetric flow rate would be 7. 5 per cent. INTRODUCTION Non-Newtonianism and eccentricity occur simultaneously in two engineering problems: (1) flow of lubricants in journal-bearings and pressure-reducing bushings, and (2) flow of non-Newtonian fluids in plastic extruders and wellbore annuli. The lubricants used for moving parts are often non-Newtonian in character — often they are plastic in behavior. A solution to the problem of flow of non-Newtonian fluids in narrow eccentric annuli is particularly pertinent to this problem. In all experimental studies of laminar flow of fluids in concentric annuli, such as in extruders and well casings, the error due to eccentricity must be estimated or studied. A number of publicationsl-4,6,7 have dealt with this problem for Newtonian fluids; however, I am not aware of work for non-Newtonian fluids. This work is directed to the non-Newtonian problem. Before the solution to the problem is given, the pertinent conclusions from the work on Newtonian fluids will be reviewed. Heyda 1 and Redberger and Charles 2 have published general solutions to the problem of the laminar flow of Newtonian fluids in eccentric annuli, apparently without knowing of the earlier work of Ca ld well 3 and Bairstow and Berry,4 which is reported by Dryden, et al. 5 Although several mathematical routes are encompassed by the work of these authors, the results appear to be equivalent. Redberger and Charles2 show that the error caused by eccentricity in concentric annuli is negligible for small diameter ratios (k < 0.5); however, for large diameter ratios (k + l), the error in the predicted flow rate can be as great as 100 per cent or more. Partial solutions to the problem are available from the work of Dryden,5 Tao and Donovan6 and Piercy, et a1.7 Tao and Donovan examined the case of flow in narrow, eccentric annuli (k + 1) with and without rotation of the annular core. These authors also reviewed previous work on this subject and verified their approach with experimental data. Dryden gives the solution for the limiting case of complete eccentricity or tangency. Piercy, et a l. published an early solution to the problem of narrow eccentric annular flow. The conclusions of Redberger and Charles2 and the experimental proof of Tao and Donovan6 both suggest that the region of large diameter ratios (k + 1) is of main interest and that the parallel planes approximation to the solution in this region is satisfactory. This method will now be extended to the laminar flow of non-Newtonian fluids in narrow eccentric annuli. THEORETICAL SOLUTION The geometrical aspects of the problem are illustrated in Fig. 1. To represent the non-Newtonian fluid the power-law model was selected. This model has many disadvantages which have been pointed out; nevertheless, its simplicity, its frequent and wide applicability justify its use in this work. Fredrickson and Bird8 and Savins9 have used it as a basis for a theoretical study of laminar flow of non-Newtonian fluids in concentric annuli.

Jan 1, 1966

By C. G. Dunn

The measurement of interfacial teusions or grain boundary energies in metals is an important metallurgical problem, especially since it bears on growth and nucleation processes. Statistical methods of measuring equilibrium grain boundary angles, which relate interfacial tensions, have been used by some investigators1&apos;2 but more direct methods would be preferred. A direct way, based on a simple extension of a successful method of growing single crystals of silicon ferrite to predetermined orientations in flat specimens,3 is to produce three-grain specimens in such a way that the equilibrium common grain boundary will be perpendicular to the surface of the specimen. The angles to be measured then appear as the grain boundary angles in the surface of the specimen. The method of producing a single crystal specimen with a predetermined orientation is basically the same as that employed by Yoshida and Fuji-wara4 in their work on aluminum wires. The specimen, prior to any single crystal transformation, must have a matrix which will support the growth of a crystal of the desired orientation. Growth may occur through exaggerated grain growth or, if the matrix is strained a critical amount. by normal recrystallization. In either case the matrix must have stability at the temperature used to effect the transformation, this stability appearing as a long induction period for exaggerated grain growth or for the formation of recrystallization nuclei. Additional control is gained by using a high temperature gradient through which the specimen is moved at a suitable rate. To obtain the desired orientation, the specimen is fed a short way into the furnace producing one or more crystals in the hot end. After the specimen is removed from the furnace, the orientation of a crystal is determined, so that this crystal may be reoriented by properly deforming a narrow piece of the matrix between the end crystal and the rest of the specimen. This part of the specimen in the case of silicon ferrite is preferably held at red heat during the reorienting process. Fig 1 shows a specimen which is ready to be transformed into a single crystal through growth of a reoriented "seed" crystal. When the method just described is applied to the production of a three-grain specimen two crystals are grown first side by side in one end, the specimen is then reversed and the third grain grown from the opposite end. A suitable group of grains each of different orientation is one where all three grains have the same crystallo-graphic plane in the plane of the specimen. Fig 2 shows a photograph of a three-grain group prepared as described. The notches are introduced in the open ends of the grain boundaries to anchor them during the final annealing operations which ultimately should bring the grain boundaries to the lowest energy configuration. Two-grain groups with different crystallographic planes in the plane of the specimen can be similarly prepared and treated. If the two grains have different surface (gas to metal) energies per unit area, the equilibrium condition leads to a curved grain boundary.* * This feature of the problem was pointed out by J. c. Fisher. References 1. Cyril Stanley Smith: Grains. Phases and Interfaces: An Interpretation of Microstructure. Trans. AIME 175, 15. Met. Tech. TP 2387, June 1948. 2. D. Harker and E. Parker: Grain Shape and Grain Growth. Trans. A.S.M. (194,5) 34, 156-195. 3. C. G. Dunn, A. Seddon, and R. Wylie: Unpublished Work, 1946-1947. 4. Takeo Fujiwara: A Method of Producing A Long Single-Crystal Wire of Aluminum with any Desired Crystallographic Axis. Jnl. of Sci. Horoshima Univ. A, (1939) 9, No. 3, 227.

Jan 1, 1950

R. W. Raymond, New York City: As was announced in the Secretary&apos;s note, appended to the pamphlet edition of Dr. Ledoux&apos;s paper, I have undertaken to superintend the preparation of the samples required by his plan, and the ollation for publication of the results reported. Promises of cordial co-operation hare been received already from a number of leading assayers;? and it is to he expected that the data thus collected, and the discussion to be based upon them, will shed much light upon the important question raised in this paper. Although a detailed discussion of methods on the present occasion might be deemed premature, I am sure that suggestions on the subject from members engaged in assaying would be timely and valuable as a preliminary to later and more detailed criticism. Herbert G. Torrey (U. S. Assay Office), New York City : I may say in relation to the losses in the furnace that I have made a number of experiments, and on my little blank form years ago I put down a place for the losses in the cupel. It met with a good deal of opposition among the smelters, but I claimed that it was my duty to give the full amount of the gold and silver present, and that it

Jan 1, 1895

By Herman Garlichs

The development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870. Lead production in Southwest Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a, V. Wood and galena were placed in the furnace and ignited.. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 it. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 1, 1918

By Herman Garlichs

THE development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately, $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870: Lead production in South-west Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 ,tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a V. Wood and galena were placed in the furnace and ignited. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 ft. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required, for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 7, 1917

By Walter O. Snelling

IN combating mine-fires the use of carbon dioxide as a means of producing an atmosphere in which combustion cannot be sustained, has been many times suggested and frequently tried, generally with a fair degree of success. The carbon dioxide is produced by acting on limestone with dilute sulphuric acid, large wooden boxes being used to hold the limestone, and arranged in such a manner that one box may, be cleaned and refilled with blocks of limestone while another is being used in generating the carbon dioxide. The gas is led by means of pipes of large diameter to the location of the fire, tight brattices having been previously put up as close to the fire as possible on every side, so as to limit the space to be filled with the .gas to the smallest possible volume. The cost of producing Carbon Dioxide has been, however, a decided draw-back to the use of this method, and the danger of producing carbon monoxide by the reduction of the carbon dioxide by heated carbon, and consequently bringing about an explosion, has also tended to prevent the application of this method. The use of sulphur dioxide in combating mine-fires has not, I believe, been previously suggested or tried, and yet the method presents such decided advantages over the use of carbon dioxide that it seems proper to suggest the advisability of considering it as a cheap, convenient, and safe means of fighting stubborn mine-fires. 1. Cost, Preparation, etc.-One ton of brimstone, costing from $20 to $30, will produce about 25,000 cu. ft. of sulphur dioxide gas, and allowing for all sources of loss it is probable that sulphur dioxide gas can be produced for about $1,300 per 1,000,000 cu. ft. For carbon dioxide gas, produced by the action of sulphuric acid on limestone, a good estimate would be $4,000 per 1,000,000 cu. ft., provided that sulphuric acid

Sep 1, 1908

By Narendrakumar A. Chevli

Exploratory work was conducted in the fabrication of integrated circuitry, specifically linear amplifier circuits, by three general methods: 1) monolithic diffused silicon; 2) a combination of metal thin-film and monolithic diffused silicon; and 3) a hybrid of metal films and diffused silicon on an alunina substrate. In these linear amplifier integrated circuits the followzng conditions were desired: very high-frequency response, high voltage gain, and good thermal tracking stability of electrical characteristics. The resulting circuit designs imposed problems of isolation between elements, layout and smallness of size of active elements, and close tolerances on electrzcal characteristics of the passive elements. Interconnection problems for specific designs resulted from the small dimensions involved and the topography of the hybrid fabrication techniques. The desired integrated-circuit characteristics were achieved with the technologies of categories 2 and 3 above. Solutions to the problems imposed by these characteristics lay in the ability to isolate czrcuit elements of small size while providing a layout designed to minimize element-to-element variations. Sufficient freedom in the formation of passive elements was achieved by uniting the metal film and the monolithic silicon technologies. The most satisfactory designs were based on the beam-lead interconnection and isolation technique. SINCE the advent of integrated circuits, major emphasis has been on fabricating digital integrated circuits. Linear circuits require high performance, high voltage, and tighter tolerance components which are not always compatible with the capability of process technology available for fabrication of these circuits into integrated form. Fortunately the growth of newer and improved processes and materials for fabricating integrated circuits has been an accelerated one. This has now made possible the translation of stringent performance requirements of the linear circuits into microminiature integrated circuits of the same performance. In the exploratory work of fabricating high-performance Linear Integrated Circuits—LIC, the following objectives were formulated: i) fabrication of high-frequency transistors such as the type 2N918 isolated on a single silicon substrate; ii) fabrication of medium-frequency transistors having a very high gain at low collector currents such as the types 2N930/2N2484 isolated on a single substrate ; iii) fabrication of tight-tolerance, high-valued resistors having low temperature coefficients of resistance and stable thermal tracking characteristics, these resistors to be fabricated on an active or passive substrate; iv) simultaneous fabrication of complementary transistors—pn and pnp-on the same silicon substrate; v) fabrication of newer active elements such as MOS, FET transistors along with the conventional active and passive elements on the same silicon substrate. State-of-the-art assessment f all the available processes, materials, and technology to meet above objectives indicated that economic fabrication of LIC cannot be achieved by a single technology for all types of linear circuits. Where design and performance of a given linear circuit can be modified and tolerated to the extent of a particular technology, then alone is it possible to fabricate a LIC using a single process technology such as all diffused, planar technology. In order to evaluate this economic breakpoint with design and performance compromise in fabricating LIC, it is essential that a thorough understanding be obtained of techniques, potentials, and limitations of all the various process technology and materials

Jan 1, 1967

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947

By D. C. Hilty, W. Crafts

A qualitative pseudoternary solidification diagram for the Fe-S-O system modified by manganese is proposed and supported by experimental derivation of an isothermal section at 1475°C and substantially 1 pct Mn in the solid-metal phase. The solubility of oxygen in liquid iron containing 1 pct Mn and sulphur contents up to 0.9 pct has been measured at 1600°C and found to increase as the sulphur content exceeds 0.15 pct. AS has been pointed out previously,&apos; all oxide and sulphide inclusions in steel, excluding mechanically entrained matter, result from modifications of the basic Fe-S-O system. Therefore, one method of attack on the problem of the mechanism of deoxida-tion and inclusion formation is to examine the influence of deoxidizers on the Fe-S-O liquidus diagram. This approach has been adopted in work on the subject being carried out at the Metals Research Laboratories of the Electro Metallurgical Co. and has resulted in the postulation of types of solidification diagrams for the Fe-S-O system modified with common deoxidizers. This method has been of considerable assistance in interpretation of the factors affecting the formation of inclusions.&apos; For the most part, however, these diagrams have been highly speculative. They were constructed primarily by inference from the pertinent binary and ternary systems and from the appearance of inclusions produced by specific deoxidizers. Moreover, since the systems contain four or more components, simplifying assumptions and qualifications were necessary in order to permit their representation as modifications of the Fe-S-O diagram. Consequently, experimental confirmation of the type of construction employed for these diagrams is desirable, and the present paper is concerned with such evidence. The addition of manganese to the Fe-S-O system was selected for initial investigation. Manganese is an important component of practically all steel and is, therefore, of fundamental interest. Because of its great affinity for sulphur, manganese has a more profound effect on the sulphide side of the Fe-S-O diagram than any of the other common deoxidizing eletments. In addition, more quantitative information pertaining to the contiguous binary and ternary systems involving iron, manganese, sulphur, and oxygen is available than for the other deoxidizers. Fe(Mn)-S-O Solidification Diagram Many of the side diagrams of interest in connection with this system are known. The Fe-Mn binary has been well established by several investigators;% the Fe-O system has been clarified by Darken and Gurry;&apos; and FeO-MnO diagrams have been published by Herty,5 Andrew, Maddocks, and Howat,6 and by Hay, Howat, and White.7 The Mn-O diagram does not appear to have been derived experimentally, but the portion of &apos;it that is of interest can be visualized easily from a consideration of the melting points of Mn and MnO and the fact that a broad miscibility gap must exist between them. The ternary Fe-Mn-O diagram has been discussed by Benedicks and Löfquist,8 Wentrup,9 and by Körber and Oelsen.10 Experimental study of the Fe-Mn-O system has been carried out by Körber and Oelsen and to a lesser degree by Chipman, Gero, and Winkler,11 Hilty and Crafts," and others. On the basis of published information, then, an outline of the Fe-Mn-O liquidus diagram can be constructed as illustrated by Fig. 1. In this, as in all succeeding diagrams, transformations such as the ?-? reaction in iron have been ignored for purposes of simplification. The arrows denote falling temperature. The distinguishing feature of this diagram is the broad region of liquid immiscibility extending

Jan 1, 1955