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By A. G. Loomis

IT is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analysis1 of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acids1,2-for example, sodium tannate or gallate-and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shut-downs. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells.

Jan 1, 1940

By C. M. Young

The safety lamp is the most common and convenient apparatus for detecting inflammable gases in mines, the presence of gas being shown by a blue flame, called the cap, if the wick has been lowered to suppress the luminous flame. The height of the cap increases with the proportion of gas and with the temperature of the lamp flame. Lamps of the Wolf type, the fuel of which is benzine, have a hotter flame than lamps in which vegetable oils are used, such as the Davy, and the Clanny, and are more sensitive than the latter and their many modifications. The Piehler alcohol lamp gives a still higher cap while the Clowes hydrogen lamp is most sensitive of all. While the effect of the temperature of the source of ignition is well known, the writer knows of no previous attempt to correlate the change of this temperature with change of the height of the cap produced, In order to determine the height of the cap at various temperatures, it was necessary to have a source of ignition the temperature of which could be accurately controlled over a considerable range. This condition was met by a coil of wire of high fusing point heated by an electric current controlled by a variable resistance. The use of a coil offered the further advantage of freedom from complications due to the flame of a burning fuel. Such a flame, being itself of variable height, would to some extent raise or lower the elevation of the base of the cap and therefore add to the difficulty of determining the height of the cap. Besides this, the presence of a small cap from the lamp fuel, commonly known as the "fuel cap," would interfere with the observation of small gas caps. After some experiment, a coil was made of platinum wire, No. 26, diameter 0.016 in. The coil was 17/64 in. (6.746 mm.) in outside diameter and had eight full turns in a length of 1/2 in. (12.69 mm.). This was connected to an electric circuit through an adjustable resistance, as shown in Fig. 1. In order to measure the temperature, a thermocouple was inserted in the center of the coil; the leads passed out at the ends and were ccnducted to a millivoltmeter. It is probable that the current of air passing upward through the coil resulted in the indication of a tempera-

Jan 1, 1920

By Henry N. Toler

Oil and gas development in Mississippi during 1936 was about the same as during the past three or four years, with less drilling activity in the proven fields; although at the end of the year there was a decided increase in interest and activity. Jackson Gas Field Six wells were drilled in the Jackson gas field, three of which were producers and three dry holes. The gas production for 1936 was 12,968,-000,000 cu. ft., which is 2,500,000,000 cu. ft. more than for any previous year. The total gas production from the field to the end of 1936 has been 58,092,000,000 cubic feet. Thirteen producing gas wells were abandoned during the year because of encroachment of salt water. At present there are 99 producing gas wells in the field. The three oil wells on the edge of the field, which had been producing, were not produccd during 1936, although they are still capable of making some oil with much salt water. The rock pressure at the end of the year was 930 lb., which is a decline of 80 Ib. since the discovery of the field. In March of 1936, the State Legislature appropriated $115,000 to be used by the State Mineral Lease Commission in drilling some gas wells

Jan 1, 1937

By J. B. Newkirk, A. H. Geisler

INTRODUCTION CERTAIN of the permanent magnet alloys provide ideal systems for the study of the kinetics of the precipitation reaction and the correlation of structure with properties. One such system, Cu-Ni-Fe, was found by Bradley1,2 to exhibit a coherent transition state in the precipitation process analogous to that reported for Al-Cu alloys somewhat earlier.3 The attractiveness of some permanent magnet alloys for study lies in the fact that vertical sections of the ternary phase diagram in certain regions of composition (Fig I) have as their prototype the binary Ni-Au diagram. Alloys of this type decompose into products that have the same crystal lattice type but only slightly different lattice parameters. The advantages that such alloy systems offer for study over the usual in which an intermetallic compound is formed are many: I. Since the precipitate has the same crystal structure as the matrix, complex atomic movements are not required to form the new lattice. 2. Similarly, complex orientation relationships are not involved for both the matrix and the precipitate would be expected to have the same orientation. 3. Small disregistry of the decomposition products at equilibrium (in contrast with Cu-Ag alloys) is conducive to extensive coherent growth in the transient state and thus the transition lattice can be detected by the usual X ray diffraction methods. 4. Finally, the relative quantities of precipitate and depleted matrix can be varied from o to 100 pct* thus permitting wide freedom for the study of the effect of composition on coherent growth and properties. In the Cu-Ni-Fe alloys of appropriate composition, the face-centered cubic precipitate and also the depleted matrix when first formed are coherent with the parent matrix.1,2 The two have the same [ao] parameter as the original matrix but they are both tetragonal; the precipitate has an axial ratio c/a < I while that of the depleted matrix is c/a > I. When coherency is lost they assume the normal face-centered cubic structure with the depleted matrix having a lattice parameter greater than the original matrix and that of the precipitate less. Such a mechanism would also be expected for Cu-Ni-Co alloys because of the similarity in constitution but this had not been demonstrated. The present investigation was conducted on a Cu-Ni-Co alloy. The constitution diagram and magnetic properties of these alloys have been fairly well established 4,5 however, no previous determinations of mechanism of precipitation and no correlation of structure with properties had been made. Thus, an alloy of this system was chosen for a comprehensive investiga-

Jan 1, 1948

By Francis Crockard

DURING the past five years we have probably witnessed greater technological advances than in any similar period. Industry and science have steadily marched ahead. The makers of iron and steel products have watched with great interest the development of stream-lined trains, faster and safer airplanes, the entirely new science of air-conditioning and the widespread use of stainless steels. Since 1930, we have witnessed the erection of the world&apos;s largest suspension bridge, the largest and fastest ocean liner and the spectacular Boulder Dam, while even greater things are planned in these particular fields. Other indus-tries, too, have been moving ahead rapidly. This advance in a few years has been caused primarily by the fierce competition of the depression. Now, more than ever, is the emphasis placed upon quality and service. Makers of southern merchant pig iron have been no exception and have been confronted with increasingly strict chemical specifications and with much greater stress on physical characteristics than ever before. For example, sulfur in the iron must be held very low, competition demanding that it be in the 0.020&apos;s and low 0.030&apos;s; silicon content must be held within a very narrow range, and definite requirements of phos-phorus and manganese are an essential part of the specifications. Physical characteristics are becoming of increasingly greater impor-tance. The introduction of triple-skimmed, slow-cooled iron several years ago was the first step in this direction. Now there are a few customers who buy iron by chemical analysis and physical appear-ance, having found that the analysis alone is an insufficient guide to their requirements.

Jan 1, 1935

By R. W. Raymond

THE death of Privy Councilor Bruno Kerl, on March 25, 1905, terminated a distinguished and useful career. Bruno Kerl was born March 24, 1824, at St. Andreasberg in the Harz, and entered in 1840 the mining school of Clausthal, where he studied for three years, working at the same time in the mines and stamp-mills. After an additional year of practice in the silver-reduction and iron-works of the Upper Harz, he passed his examination as a metallurgical graduate, and studied for a year at Göttingen under WV filer in chemistry, Hausmann in mineralogy, and eminent teachers in other branches. In 1846 he was employed at the Oker works, but very soon left this post, to become a tutor in chemistry, metallurgy, etc., at Clausthal, where he continued to labor until 1867. During this period the Clausthal school became a completely equipped Mining Academy, and Kerl was made in 1862 a full professor. Meanwhile, in addition to the work of instruction, he discharged, simultaneously or successively, the duties of many responsible official positions in the Royal Hanoverian administration of mines and smelting-works, and also published many valuable books and treatises. Among these were professional guide-books to the Upper and Lower Harz, and their characteristic metallurgical processes; a manual of qualitative and quantitative blow-pipe analysis; another of metallurgical assaying ; and, most important of all, a Handbook of Metallurgy in four volumes, the second edition of which was issued in Leipzig, 1861-1865. This book was speedily recognized as the leading authority in its field. In this country, the English translation and revision, by Crookes and Röhrig, published about 1869, had a large circulation. In addition to these literary labors, Prof. Kerl became in

Jul 1, 1905

By B. Trentini

In the spectacular development of pure oxygen steel-making, the process using the vertical lance converter LD, is at the present time the most widely employed. Proper control of slag composition during the steel-making process appears to be essential in achieving satisfactory blowing from both the metallic yield and metallurgical points of view. The paper illustrates the primary importance of the presence of a large quantity of metal droplets in the slag during the process. In the case of both phosphorus and hematite pig iron, it can be deduced from the phase diagrams and confirmed by experimentation that nonhomogeneous slags are one of the causes of slag overflowing during the blow. The problem is however a complex one and further physicochemical studies appear necessary. Finally, the new continuous steelmakingprocess developed by IRSID is described. PEOPLE who knew Henri Marion Howe have said that he took great pleasure in speculating on the future of metallurgical processes. It is therefore not inappropriate to devote, in his memory, some description and discussion to processes unknown to the world of his time, in particular oxygen steelmaking and continuous steelmaking. The first industrial application to steelmaking of tonnage oxygen produced by air liquefaction was made in Germany just before the war and consisted in enriching the air blown through the bottom of a basic Begsemer converter in order to melt a higher proportion of scrap and to produce steels with lower nitrogen content than is achieved with conventional practice. While this process was being developed after the war, mostly in Western Europe, steelmakers were becoming increasingly familiar with the technique of blowing pure oxygen from the top, first by means of consumable steel pipes, with or without refractory shielding, and later by water-cooled lances, designed for the purpose and affording longer life. The field was then open for the wide use of pure oxygen in steelmaking, either in existing processes such as open-hearth or electric furnace, or in new processes. These new processes can be broadly classified according to the category of furnace employed. In the case of the vertical converter taken as the first category, bottom-blowing of pure oxygen causes extremely rapid wear of the refractory tuyeres, and although various expedients have been tried to overcome this drawback (such as mixing oxygen with CO2 or H2O or using high pressure oxygen), they have had to be abandoned. The solution for vertical converters has been found in top-blowing with a vertical water-cooled lance; this is known as the LD process or basic oxygen converter process.

Jan 1, 1969

By R. W. Callen, W. A. Hockings

This paper describes a computer program which calculates material balances for complex steady-state material flow circuits encountered in mineral processing. The program determines mass flows in the various process streams of a flowsheet from multicomponent analytical data obtained from samples of the streams. The program, Metallurgical Balance System (MBS), has been used extensively in treating Pilot plant test data, in production evaluation and control, and in plant design. The program performs well even on ill-conditioned data. Input to the program is easily accomplished by unskilled personnel and the output appears in well-formatted tables.

Jan 1, 1981

By W. B. Gogarty

The reported decreases in water mobility do not seem unusual in view of non-Newtonian fluid properties. Shear stress vs shear rate diagrams have been reported for other solutions of water-soluble polymers. Some of these polymers are similar to the type mentioned by the author. Generally, the shear stress-shear rate is a non-linear function for these solutions. Data for plotting apparent viscosity vs shear rate can be obtained from this function. Apparent viscosity is defined as the ratio of shear stress to shear rate at a given shear rate. When plotted, the apparent viscosity decreases with increasing shear rate. This behavior is typical of a pseudoplastic fluid. For some water-soluble polymer solutions, the apparent viscosity decreases more than 50 times while the shear rate increases 1,000 times. Thus, viscosity of a pseudoplastic fluid only has meaning at a specified shear rate. Results of Fig. 1 could be explained in these terms. Viscosities measured in the Ostwald viscometer represent values at a given shear rate. Some average shear rate is affecting the polymer solutions while flowing through the core. This average value fixes the apparent viscosity as long as the flow rate remains constant. Viscosities measured by the two methods will be equal if shear rates are the same. The results indicate that shear rate in the core is lower (higher apparent viscosity) than in the viscometer. In the paper by Johnson, Bossler and Naumann, the relative permeability is independent of viscosity ratio. Thus, the relative permeability with respect to water flow at residual oil should be independent of the flowing phase viscosity. Polymer solutions will appear as Newtonian fluids The discussion emphasizes the nature of the "resistance factor effect" as discussed in the paper. Repeated anomalies arising in hundreds of experiments led us to the conclusion that non-Newtonian flow is not the only factor. Several of the key anomalies are as follows: 1. Measured viscosities over a range of shear rates from <1 sec-&apos; to 1,000 sec-&apos; do not account for but a minor fraction of the R observed in cores when compared in similar shear-rate ranges. 2. The slope of R vs flow rates in cores is always different from that expected from viscometer shear-rate measurements as shown in Fig. 2. in a core, the level of viscosity being fixed at a given flow rate. With these conditions, the definition of resistance factor R by Eq. 2 is simplified to Since , is constant with rate, R becomes a measure of the apparent viscosity in a core at a given flow rate. Variation in flow rate could easily account for the changes of R shown in Fig. 5. Also, this points to the fallacy of assuming R to be a unique parameter. The constant resistance factors at different flooding velocities appear to be in disagreement with the above discussion. The author furnishes Fig. 2 to support his arguments. As shown, the resistance factors remained substantially constant in the two cores over a considerable range of flooding velocities. However, in the 73-md core, the factor increases at lower rates. This behavior agrees with known characteristics of some pseudoplastic material. These materials act both as Newtonian and as non-Newtonian fluids in different regions of shear rate. Some exhibit first Newtonian, then non-Newtonian, finally, Newtonian character. Others are first non-Newtonian and then Newtonian. This latter type would explain the results with the 73-md core. The Fann-instrument results are not significant since shear rates in the core may be much different than with the viscometer. The higher resistance factor at high rates in the 150-md core is more difficult to explain. The greater resistance at increased flow rates could be attributed to what might be termed temporary bridging. As envisioned, changes in polymer configuration occur at the higher energy associated with the increased flow rate. These changes could cause less effective passage of polymer through the core. Correspondingly, increases in pressure drop will occur. These will be interpreted as higher resistance factors. 3. Most polymer solutions are non-Newtonian and many are more shear-rate sensitive than the polymers in question, yet only a very few polymers demonstrate useful R values. Gogarty&apos;s assumption that viscosities in cores and vis-cometers will be the same if measured at the same shear rate is only valid if non-Newtonian rheology is the only parameter. The experimental evidence does not validate this assumption. The anomalies observed in the equilibrium displacement experiment shown in Fig. 5 are not explained on the basis of varying flow rates since the rates were held constant. M

Jan 1, 1965

By AIME AIME

NO MORE SUITABLE time and place than LOS Angeles on Thursday and Friday, July 28 and 29, could have been chosen for the Western Regional Meeting of the~1nstitutk. After attending two clays of technical sessions and enjoying the luncheons and dinners of the meeting, visitors, on the following days, could see the opening ceremonies and events of the Olympic Games, which started on July 30 and continued to Aug. 14. Such d spectacle can be seen only once in a generation in this country.

Jan 1, 1932

C. P. BOWIE, San Francisco, Cal.-In my work with the U.S. Bureau of Mines, I have been detailed to report on oil storage containers, and in going around the country I have, been much interested in, the possibilities in the use of concrete for such containers. In talking with a good many people, I have discovered that concrete is being used A good deal for a wide variety of oils ranging from 14° to as high as 40° Bé., especially, by some of the western railroads:, If any member has had experience, in storing gasoline in concrete, I should like to learn of it. DORSEY HAGER, Tulsa, Okla.-Mr. M J. Munn, formerly .with the U. S. Geological Survey, acid connected with the Gypsy Oil Co., until a short time ago, has invented a invented a method for the application of concrete to the storage not only of crude oil but of refined products:. The Cosden Oil Co., of Tulsa, is now working on that plan, and, expects to store refined products in concrete tanks. THE CHAIRMAN (I.N. KNAPP, Ardmore Pa.).-I have had considerable experience in building masonry tanks for gas Holders. I do not believe it is possible to build a concrete or masonry tank of any kind. With hydraulic cement, mortar, which will be absolutely water-tight, unless the bottom and inner wall, after completion are waterproofed with some impervious material. The same will be true of oil tanks, the bottom and inner face of which must be made impervious to oil. Masonry tanks are intended to be sunk in the ground. All that the wall of the tank then amounts to is a retaining wall to keep the excavation in shape and to receive an impervious coating. The bottom of, a; tank, when empty, must be protected by a relief valve from any hydraulic: pressure acting from below. At ordinary prices, for sheets, a tank 100 ft. diam by 20 ft. deep can be built of steel much quicker and cheaper than of masonry. Several years, ago I saw very large oil storage tank under construction in California the bottom and sides being concrete. The sides were, sloped at about the single of repose for the material excavated: If you build a steel oil tank, you can get. .men for the work who do nothing else, and you, are likely to get a satisfactory job; but if you wish to build a concrete or masonry tank it is almost: impossible to find men skilled in building absolutely water-tight masonry Work. The general idea is that any laborer can mix up concrete in any old way and make a,

Jan 1, 1918

By W. B. Coleman

Considerable discussion on the effect of iron and steel scrap in blastfurnace burdens was presented in the January, 1927, issue of Mining and Metallurgy. Therein the question is asked as to what causes the difference in physical properties of pig irons where the chemical analyses are practically the same. This point no doubt has been noticed by a number of furnace operators, but several years ago very little thought was given to it. The foundries purchased pig iron, had it analyzed and found it to be within their specification. The castings made from this iron at times would be satisfactory and at other times hardness and shrinkage would occur. Since the iron was chemically correct the foundries generally were at a loss as to what to do. They changed their method of melting in the cupola and in some cases this corrected the trouble. In some instances the foundry would continue eliminating a brand of iron until the castings produced were satisfactory. Through this process of elimination they would finally arrive at the conclusion that a certain brand of iron was causing the trouble. During the course of this elimination minor changes might have been made in the melting and in the end satisfactory castings were secured without discovering any definite reason for the trouble. Frequently the foundries blamed the manufacturer of the pig iron although the seat of the trouble was in their own method of melting. I have in mind one foundry in particular that was using three brands of pig iron for producing their castings and their losses were rather high. Three entirely new brands of iron were substituted in the charge and still the losses continued. Even after using six brands of pig iron the management felt that the pig iron was the cause. The difficulties encountered in the melting of iron in the cupola, over the past several years, reflect in a great many cases on the operation of the cupola. At different times certain brands of iron were unsuitable for producing a certain class of castings, but at the same time one could see no reason why the iron should be considered abnormal. Irons from furnaces where production and low cost are the main factors that are being used in foundries produce in most cases harder cast-

Jan 1, 1927

By H. L. Talbot, A. J. Hall, R. S. Young

A METHOD for the chemical differentiation of oxidized cobalt from sulphide cobalt in complex mine and concentrator products is of considerable interest to a number of mining companies throughout the world. At Rhokana Corporation, in Northern Rhodesia, for instance, cobalt is found chiefly in the sulphide form, as carrollite, but a cobalt oxide mineral also occurs irregularly underground, and relatively small quantities in the mill feed from time to time are difficult to detect it visually at the concentrator. The oxide cobalt is not amenable to the sulphide flotation process used at Rhokana and nearly all of it passes into the tailing. The occasional. period when high tailing losses occur with no appreciable change in the cobalt content of the mill feed has naturally been disturbing to the concentrator staff, who had no means of determining whether an influx of cobalt oxide ore or laxity on the part of the mill flotation operators were responsible for these results. A procedure for determining oxidized copper minerals, based on their solubility in dilute sulphuric acid saturated with SO2, has been used for many years in the copper industry. In the presence of cuprite the procedure fails, but otherwise it gives results quite satisfactory for control purposes. Empirical methods for determining oxidized forms of zinc and lead have been proposed, but they are generally unsatisfactory except in isolated cases of a very simple ore. No published procedure for determining oxidized forms of cobalt or similar elements has come to the authors&apos; notice. EXPERIMENTAL PROCEDURE There are obviously two alternatives in attacking a problem of this nature. One is to employ a solvent for oxide cobalt that will not dissolve cobalt sulphide. The other is, to find a substance capable of oxidizing the cobalt sulphide to sulphate, which of course is water-soluble and can then be leached from the water-insoluble oxide cobalt. A representative sample of Rhokana cobalt oxide ore was secured, ground to minus 200-mesh, and carefully rolled to furnish a standard sample for this work. The analysis of this material gave the following percentages: Co, 0.55; Cu, 1.64; Fe, 2.98; S, 0.08; SiO2, 41.42; A1203, 11.20; CaO, 13.82; MgO, 3.80. As a source of cobalt sulphide a similar large sample of carrollite was prepared, analyzing Co, 23.36 per cent; Cu, 27.32; and S, 31.13. This sample of course was not pure carrollite, but was the best obtainable in quantities sufficient for a standard intended for considerable work. It was a pure sulphide sample, microscopic examination showing only carrollite, a little bornite, and gangue, with no visible sign of oxidized ore present. A wide variety of reagents were used in an effort to selectively dissolve oxide cobalt or to oxidize sulphide cobalt to

Jan 1, 1946

By R. E. Mussler, F. E. Block, T. T. Campbell

An exploratovy study was made to deternzine the feasibility of preparing beryllium by the metallother-. mic reduction of beryllium oxide. The procedure involved heating a relatively nonvolatile metal reductant in contact with beryllium oxide in a vacuum. Beryllium vapors formed in the reaction were condensed as a coherent deposit on a heated surface. Reductants tested included tanthanun, yttrium, thorium, Th-Mg, and Zr- Ti alloys, and the hydrides of lanthaniir~z, yttriunz, and zirconiur?7,. Test ten7pevatures ranged from 1350&apos;to 175O&apos; C, and reaction times ranged frot 30 to 100 lzr. In most cases metal recoveries were lola, although yields close to 90 pct of theoretical were obtained with latzthanum, yttrium, and zirconium reductants. In most cases metal deposits were contanzinated by beryllides, /ls/cally of the Beln M or Bel3 M type. BERYLLIUM has a variety of unique properties including light weight (sp gr 1.85), low thermal neutron absorption cross section, high scattering cross section, excellent dimensional stability, high strength to weight ratio, high melting point (1285"C), high specific heat, and high thermal conductivity. Interest in beryllium as a structural material in aerospace and nuclear-reactor applications is based on these properties. In general, the potential of beryllium has been only partially realized, largely because of the brittleness of poly crystalline forms of beryllium, difficulties associated in its fabrication, and joining problems encountered in its use in structural applications. Several excellent books and monographs are available to those interested in the occurrence, extractive metallurgy, and utilization of beryllium.1"* Although an extensive amount of research on beryllium has been in progress during the past 10 years, much of the work has been concerned either with the so-called "ductility problem" or with the development of methods of fabrication and evaluation of properties of various commercial or purified grades of metal. A recent survey of the literature indicates that only limited efforts are presently being directed toward developing new methods for reducing beryllium compounds to metal. Two major commercial methods now used to produce beryllium are the magnesium reduction of beryllium fluoride and e lec trow inn ing of beryllium from fused sodium chloride-beryllium chloride salt baths. Only a limited amount of work has been done on the direct reduction of beryllium oxide. Major factors which complicate this method are the great stability of beryllium oxide and the reactive nature of beryllium metal. The stability of the oxide necessitates extremely high reduction temperatures and vacuum operation to liberate beryllium metal vapor and cause reactions of the following type to proceed: XBeO(s) +YM(s)-MYOX(s) + XBe(& As early as 1939, roll&apos; used this reaction for the direct reduction of beryllia by zirconium and titanium, and later in 1952 ~a~el~ studied the reduction of beryl-

Jan 1, 1967

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

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke&apos; first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer&apos; who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier&apos; gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By Francis Crockard

DURING the past five years we have probably witnessed greater technological advances than in any similar period. Industry and science have steadily marched ahead. The makers of iron and steel products have watched with great interest the development of stream-lined trains, faster and safer airplanes, the entirely new science of air-conditioning and the widespread use of stainless steels. Since 1930, we have witnessed the erection of the world&apos;s largest suspension bridge, the largest and fastest ocean liner and the spectacular Boulder Dam, while even greater things are planned in these particular fields. Other indus-tries, too, have been moving ahead rapidly. This advance in a few years has been caused primarily by the fierce competition of the depression. Now, more than ever, is the emphasis placed upon quality and service. Makers of southern merchant pig iron have been no exception and have been confronted with increasingly strict chemical specifications and with much greater stress on physical characteristics than ever before. For example, sulfur in the iron must be held very low, competition demanding that it be in the 0.020&apos;s and low 0.030&apos;s; silicon content must be held within a very narrow range, and definite requirements of phos-phorus and manganese are an essential part of the specifications. Physical characteristics are becoming of increasingly greater impor-tance. The introduction of triple-skimmed, slow-cooled iron several years ago was the first step in this direction. Now there are a few customers who buy iron by chemical analysis and physical appear-ance, having found that the analysis alone is an insufficient guide to their requirements.

Jan 1, 1936

By J. J. Lander, L. H. Germer

MOLYBDENUM and tungsten have desirable corrosion and temperature resistant properties, but the metals in bulk are expensive and their fabrication is difficult. Such considerations led to a search for a method of plating them upon base metals. This search was successful and led furthermore to a number of developments which could not have been foreseen. Neither pure tungsten nor pure molybdenum has been electroplated successfully, although the literature of electroplating is liberally sprinkled with the description of unsuccessful attempts. The process of plating these metals by thermal reduction of their halides has achieved only limited usefulness because of technical limitations and because of limited range of product quality. Plating by thermal decomposition of the carbonyls does not suffer from limitations of the same sort and the properties of the plate are readily controllable. This paper describes the plating of molybdenum and tungsten, and of compounds and alloys of these metals, by pyrolysis of their carbonyl vapors. Chromium also has been plated in this manner, but the experiments upon chromium have been less extensive and the results much less satisfactory. Probably the most important of the products which we have obtained are the alloys with carbon, and the carbides of the metals. Either molybdenum or tungsten can be deposited upon a base metal as a coherent and adherent coating. By adjusting the plating condition the carbon content of the coating can be made to have any value from substantially zero to about 35 atomic pct. The hardness is dependent primarily upon the amount of carbon in the plate and can be regulated over a very wide range, some coatings containing considerable carbon being harder than sapphire. In addition to products already known this method of plating has yielded new carbides of molybdenum and tungsten and alloys supersaturated with carbon. These new products are possible because, in the process of plating, carbonyl can be decomposed at temperatures as low as about 150&apos;C, and thus in the presence of other substances reactions occur which could perhaps not be produced in any other way. In addition to carbides and alloys with carbon, sulphides and oxides of molybdenum and tungsten have been produced and studied. There are certain other advantages of the carbonyl method of plating. It is not required that the base have good electrical conductivity as in electrochemical processes, and the base need not have the temperature stability required in plating from a halide. Thus low melting glasses, as well as other ceramics, can be plated almost as readily as metals. In particular, the plating of glass with

Jan 1, 1947

By Leroy Palmer

ALL the domestic. production of magnesite during 1925 came from two states, California and Washington. Of a total of 120,660 tons of crude ore, 64,600 tons, or 54 per cent., were produced in California.1 Of .this quantity California produced about 99 per cent. of the caustic calcined, but only 10 per cent. of the dead-burned. The largest producer was C. S. Maltby, of San Francisco, who operated the Red Mountain mine, in Santa Clara County, and the Sampson mine, in San Benito County, under lease. These two mines have been studied by the author, and offer interesting comparisons as to mining and treatment methods and final products. GEOLOGY The general geology of the magnesite deposits of California has been described by Hess,2 Bain3 and others,4 and although a detailed discussion is not necessary here, a brief summary will assist in understanding mining conditions. California magnesite, when comparatively pure, is usually a white, fine-grained rock, with a conchoidal fracture, occurring in veins and lense-like masses in serpentine. The veins vary considerably in width, and usually occur in a series of more or less parallel veins intersected by other series or systems of veins, probably following original or secondary fissures in the enclosing serpentine. The most generally accepted theory of origin is that the magnesite was formed by the action of surface waters charged with C02 percolating downward through fissures and changing the magnesium silicates of the serpentine into magnesium carbonate.

Jan 1, 1927

By Leroy A. Palmer

All the domestic production of magnesite during 1925 came from two states, California and Washington. Of a total of 120,660 tons of crude ore, 64,600 tons, or 54 per cent., were produced in California.&apos; Of this quantity California produced about 99 per cent. of the caustic calcined, but only 10 per cent. of the dead-burned. The largest producer was C. S. Maltby, of San Francisco, who operated the Red Mountain mine, in Santa Clara County, and the Sampson mine, in San Benito County, under lease. These two mines have been studied by the author, and offer interesting comparisons as to mining and treatment methods and final products. Geology The general geology of the magnesite deposits of California has been described by Hess,2 Bain3 and others4 and although a detailed discussion is not necessary here, a brief summary will assist in understanding mining conditions. California magnesite, when comparatively pure, is usually a white, fine-grained rock, with a conchoidal fracture, occurring in veins and lense-like masses in serpentine. The veins vary considerably in width, and usually occur in a series of more or less parallel veins intersected by other series or systems of veins, probably following original or secondary fissures in the enclosing serpentine. The most generally accepted theory of origin is that the magnesite was formed by the action of surface waters charged with CO2 percolating downward through fissures and changing the magnesium silicates of the serpentine into magnesium carbonate.

Jan 1, 1927

By Josiah Royce

To evaluate chemically the sample of rock obtained by diamond drilling, it has long been recognized that the analyses of the two components of the sample, core and sludge, must be given appropriate influence in computing the average analysis of any unit of depth. The purpose of this investigation is to set forth what means are available for apportioning the effect of core and sludge on the final analysis, what variables affect the problem, and what combination of applied mathematics will closest approximate the truth under each condition as these variables proceed within their limitations. A drill hole is bored in iron ore exploration principally to test variations in rock composition with depth and is usually directed as nearly normal to the bedding of a horizon to be tested as possible. This practice has a tendency to minimize variation in composition laterally which in any event is not likely to be great. It is obvious that the opportunity for change in analysis of a particular rock is not statistically as great radially in a diamond drill hole where the distance in which such a change may occur is from 0.719 in. (EX bit) to 1.469 in. (NX bit) as there would be longitudinally even in a&apos; run as short as 5 ft. Variations in composition of bedded or layered rocks are usually greater normal to the bedding than parallel thereto. Even in massive rocks, like porphyries, variations are functions of distance. Hence. in either case, variations along the hole are of greater effect than across it. Let us examine Fig 1 briefly to observe a cross section of a unit of depth of a typical diamond drill hole. If we neglect radial change in chemical composition, which we have seen is small compared to lengthwise variation, we can see that if core recovery was 100 pct, the core and its surrounding area, which would be recovered as cuttings (assuming 100 pct sludge recovery), must analyze the same if the sampling is perfect. This is the foundation of this paper, namely, that if core recovery is complete we may assume that the core constitutes as nearly as possible a perfect sample of the ground drilled. Now let us pass to the methods of weighting core and sludge in the final analysis and then develop each in turn. One might employ core analyses only, sludge analyses only, or apportion the influence of each by one of several methods. The most common apportionment is by direct proportion to relative theoretical vol- &apos; ume occupied by each component in the cylinder hollowed out by the drill, known as the Longyear formula. Another logical treatment would be to consider core and sludge in the final analysis according to the weight of each recovered. This procedure was elaborately set forth and refined by R. S. Moeh1man.l Then to be sure that we have embraced all the possibilities, we must admit that some other method or methods may be devised empirically or by mathematical maneuvers. Should a drill machine be capable of recovering 100 pct of the core in all types of rock, certainly core alone need be analyzed and no complicated mathematics are required; but although some companies have had fair success in obtaining high percentages of core in certain homogeneous ores on the Mar-quette Range, their same methods have proved disappointing on the Menominee, Cuyuna, and Gogebic Ranges where the iron formation often varies widely from flinty chert beds interstratified with soft hematite to wholly leached ore material composed of an unpredictable mixture of hematite and limonite with occasional zones of sugary, recrystallized chert. In spite of numerous mechanical improvements in core barrels, few drilling programs can count on complete core recovery. The sludge alone might be analyzed but for practical reasons this is inadvisable when core is obtained due to the numerous opportunities for contaminating or losing portions of the cuttings. The Longyear formula involves a weighting of the core and sludge in proportion to the theoretical volume of each, that is, where the volume of the core recovered is one-third of the total cubic volume of the cylindrical hole made by the drill, the analysis of the core is given one-third of the weight in the final analysis. This approach to

Jan 1, 1950