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By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By A. F. Baker, E. R. Palowitch, A. W. Deurbrouck

As air-pollution regulations become increasingly more stringent, increased significance is being placed on the amount of sulfur present in coals used for steam generation. These regulations are aimed at minimizing the pollution of the atmosphere with noxious gases such as the sulfur oxides that are formed and emitted when coal is burned. Two meet these future requirements, a definite need exists to reduce the sulfur content of some of the coals used for steam generation. Reducing pyritic sulfur involves liberating the pyrite from the coal and then removing it. The specific gravity of pyrite is high (5.0) compared to that of coal (about 1.2, mineral-free), and standard coal-washing devices, such as wet concentrating tables, will efficiently remove pyrite particles larger than about 100 mesh. Particles below this size will be entrained in the table water and will be carried into the clean coal product. Techniques such as froth flotation are of little benefit for pyrite reduction because the flotation characteristics of pyrite are similar to those of coal.

Jan 6, 1966

By Thomas T. Read

Jan 1, 1913

By Fred D. DeVaney

DURING the past few years a radically new process for the magnetic roasting of iron ores has been investigated and developed by Pickands Mather & Co. and the Erie Mining Co. in the Erie laboratory at Hibbing, Minn. This process, originally devised by Dr. P. H. Royster of Washington, D. C., involves the use of a roasting technique quite different from older methods. It has now been demonstrated that iron-bearing materials can be roasted as effectively as by any previously known method, and at a much lower cost. The increasing shortage of highgrade iron ores in this country has accelerated the search for new methods that would permit low grade materials to be utilized. The concept of magnetically roasting low grade nonmagnetic ores such as the oxidized taconites and then separating such material magnetically has always had considerable appeal. The magnetic concentration idea is attractive because of the sharpness of the separations and cheapness of the method. Heretofore, however, the equipment and the processes available for the magnetizing-roasting -step have left much to be desired. The customary equipment available for reduction roasting has been: 1-multiple hearth furnaces, 2-rotary kilns, and 3-shaft type kilns. In addition, it is understood that some work has been done in magnetically roasting fine ores by a process using the FluoSolids principle, but little information on this process is available. The multiple hearth kiln has been used the most but first costs and operating costs have been high because of low capacity, high maintenance, and poor gas utilization. Magnetic roasting can be done in a rotary kiln, but the radiation losses are high and the conversion to magnetite is usually unsatisfactory because of poor contact between the gases and the solids. Of the shaft-type furnaces, probably the most efficient yet developed is that designed by E. W. Davis of the Minnesota Mines Experiment Station. This furnace was operated at Cooley, Minn., during 1934-1937 but was abandoned in 1937 because the operation was uneconomic. Heretofore the basic concept behind most magnetic roasting processes has been the idea of heating iron ore to a temperature of 800° to 1100 °F in a strong reducing atmosphere, preferably either carbon monoxide or hydrogen. Temperatures under 800°F were undesirable since excessive roasting time was required. Temperatures over 1100°F were avoided because of the danger of converting part of the iron to ferrous oxide which is nonmagnetic. In the new roasting process, the operation is carried on in a shaft furnace using a controlled atmosphere containing a low percentage of reducing gas. The temperature in the roasting zone is considerably higher than with the usual reducing gas and this speeds up the reduction time. Portions of the spent furnace gases are cooled and recirculated and this together with the good contact between ore and gas makes for high reducing gas utilization. High heat economy is secured by recuperating heat from the roasted ore by passing the cold reducing gases countercurrent to flow of ore. The heat transfer principle is similar to that employed in a pebble stove and to that used in the Erie Mining Co. furnace at Aurora, Minn., for pelletizing fine magnetite concentrates derived from taconite. The theory of controlled atmosphere during the roasting operation can best be appreciated by inspecting the equilibrium diagram of the Fe-C-O system shown in Fig. 1. An inspection of this diagram shows that in certain areas magnetite, Fe3O4, is the only stable form of iron. A further inspection of this table shows that if the proper ratio is maintained between carbon dioxide to carbon monoxide, such a gas will be reducing with respect to hematite, Fe2O3, and will be oxidizing with respect to both ferrous oxide, FeO, and iron, Fe. It should be kept in mind that the formation of ferrous oxide in a roasting operation is harmful, since this oxide is nonmagnetic; if it forms in any quantity, it will cause substantial loss of iron in the ensuing magnetic separation step. If a ratio of approximately three parts carbon dioxide to one of carbon monoxide is maintained, the resulting operation can be carried on at a relatively high temperature without fear of over-reduction. Specifically, most of the tests in the Erie furnace have been made at a temperature of 1500° to 1600°F, with an entrant gas containing approximately 5 pct carbon monoxide and 15 pct carbon dioxide, with the remainder largely nitrogen. It should be remembered that the ratios of carbon monoxide to carbon dioxide shown in Fig. 1 hold even though the bulk of the gas is an inert gas such as nitrogen. It may surprise many to learn that a gas containing as low as 3 pct carbon monoxide, and 12 pct carbon dioxide with the remainder nitrogen is an extremely effective reducing gas in the 1000° to 1600°F temperature range. The reducing gas is not limited to carbon monoxide, and mixtures of hydrogen and carbon monoxide may be used effectively, provided that a similar ratio is maintained between the reducing gases and carbon dioxide and water vapor. For a more detailed explanation of the theory involved, the reader is referred to U. S. patents 2,528,552 and 2,528,553. From a safety standpoint, the weak reducing gas used in the furnace offers an advantage. Its composition is such that it is well below the limits of explosion should air enter a hot furnace. This condition is not true with the usual reducing furnace, in which a gas rich in carbon monoxide or hydrogen is used. The general furnace design and method of operation may best be understood by an inspection of

Jan 1, 1952

By Persifor Frazer

INTRODUCTION For various reasons I have not specified the locality where the research indicated in the following pages was undertaken. It will suffice to say that it was on the grounds of a villa once remote from, but now completely surrounded by, its neighboring city, and in close proximity to an industrial establishment of great extent and importance manufacturing many kinds of steel articles and employing upwards of thirty chimney-stacks for power and process work. The problem was to discover the cause or causes of the mortality to trees and plants on the place, and to trace these causes to their origin. Before undertaking this experimental work, the bibliography accompanying this paper was compiled and studied. It appears from an examination of the careful scientific work performed by the ablest French, German, and English chemists during the last 25 years that they are unanimous in assigning the principal-in fact, the overwhelmingly predominant-cause of the destruction of vegetation to sulphur oxides, resulting either from direct- oxidation of sulphur in oil of vitriol works, etc., or from the oxidation of the sulphur from the minerals associated with commercial coal. Schröder and Schertel showed in 1884 that the sulphates deposited upon the leaves are not injurious to the plants; and Freytag proved that free sulphuric acid could not be found

May 1, 1907

By R. W. Raymond

It is impracticable to prepare for the present number of the Bi-Monthly Bulletin a detailed account of the memorable Joint Meeting of the Iron and Steel Institute and our Institute, held in London, the last week in July, and of the, innumerable festivities, entertainments and excursions which accompanied and followed it, in England, Scotland, Wales and Germany. This preliminary sketch, from which all " useful particulars "' have been carefully omitted, is published unofficially, as a convenient answer to the manifold inquiries of members who did not go, and who are now trying to alleviate their unavailing regret by indulging their curiosity. Perhaps they secretly hope to hear that they did not lose so very much, after all-that the affair was not all that could have been desired or dreamed; that there were serious drawbacks, shortcomings and disappointments; and that it is just as well to have stayed it home, and now to hear about it. Let them lay no such flattering unction to their souls. The month they have missed would have been the time of their lives. They will never, never know how good a time it was, or adequately repent of their folly, if they could have gone with us, and voluntarily did not go of course, those who would but could not, have our immeasurable pity, without blame. I shall present here no consecutive and minute story, but only a series of general paragraphs concerning different aspects and stages of our experience. THE WEATHER. The proverbial good fortune of the Institute attended its visiting members and guests at every stage of the late London meeting and the numerous excursions which accompanied or followed it. Even the process of crossing the Atlantic was made delightful by smooth seas, through which the great modern transatlantic liners made their way without disagreeable

Sep 1, 1906

By GEO H. DEIKE

NOT much activity has been evident during the past year in the establishment of co-operative scholarships but the interest among the coal-mining companies is more pronounced than ever. This is apparent from the replies received to a letter sent out by the Committee on the Promotion of Student Interest in Coal Mining to over 120 coalmine operating officials. With that letter was forwarded a bulletin issued by the school of mineral industries of The Pennsylvania State College entitled ?Industrial Scholarships ? a Partnership of Industry and Education.? In that circular was outlined the need for trained men in the war and postwar world, and particularly as such demands pertain to the growth of the mineral industries.

Jan 1, 1943

By FREDERICK W. BRADLEY

MINING is one of the world's oldest industries and has pioneered the civilization of all new lands. Today, mining is not only one of the essential and basic industries of the world, but it is constantly growing in magnitude and becoming more important. We think that the most of our mining is done in the western portion of this country, but in the old State of Pennsylvania mines and products derived from minerals account for about two-thirds of the entire productive wealth of the State. As our forests are denuded, mining furnishes substitutes for timber in the way of concrete, gypsum board, etc. ; and as civilization increases the wants of mankind, mining is producing metals and minerals of every kind in increasing quantities. For example: during the past ten years the per capita consumption of copper in the United States has increased 49 per cent, to 14.56 Ib.; that of lead has increased 35 per cent, to 12.24 lb.; and that of zinc has increased 70 per cent, to 9.57 Ib. The consumption in European countries is about one-half of this, and there are other countries with large populations where there is virtually no consumption; so when all other countries catch up in consumption with our country, you can see what an enormous demand there is going to be for the metals, even to the extent of having to find substitutes for copper, lead, and zinc.

Jan 1, 1929

[A AALSETH, EARL P GEOLOGIST. AMERADA PETROLEUM CORP. BOX 1498 BILLINGS. MONT ABADIE, HENRY G ASST TO SUP OF OPER LONG BEACH OIL DEVEL. CO. 255 S. SANTA CLARA. LONG BEACH, CALIF. ABBE. TRUMAN W. … ASST.FLD.SUP.OF PROD SUN OIL COMPANY BOX 66 STOWELL. TEXAS ABBOTT. J. L. .... GEOL. PARTNER PRITCHARD & ABBOTT 504 CENTURY BLDG. FORT WORTH, TEX ABBOTT, RICHARD H OWNER ABBOTT AND HOWARD OIL 422 W. HERMOSA DR. SAN ANTONIO, TEXAS. ABBOTT, SETH J.. JR PETR ENGR.]

Jan 1, 1961

By H. M. Howe, A. G. Levy

§ 1 Introduction.—This paper gives the results of our micro-graphic determinations of the position of Ae3 in a series of 14 hypo-eutectoid steels of varying carbon content, one of them very rich in phosphorus, and of SEe for one hyper-eutectoid steel. We have proceeded chiefly by noting the temperature at which the reabsorption of the pro-eutectoid element is found to be complete after a 30-min. holding, but in part also by noting the temperature at which its precipitation begins. Observations on these same steels by Messrs. Burgess, Crowe, and Rawdon, of the United States Bureau of Standards, are given in a paper1 issued simultaneously with this, while in a third paper2 one of us compares these data with those of earlier observers. These three papers are treated as one whole by numbering their sections, tables, and illustrations continuously, and by setting the folding plates of micrographs at the end of the last paper. The Composition of the Steels Experimented On is given in Table I. § 2. Notalion and Definitions.—Following Osmond's development of Tschernoff's notation, in which " Ac3 " is the upper limit of the hypo-eutectoid part of the transformation range as observed in heating up, and " Ar3 " is that same limit as observed in cooling down, and following the usual custom of calling the upper limit of the hyper-eutectoid part of that range " SE," we may go farther and call this latter limit " SEc" when observed in heating up and " SEr " when observed in cooling down. Further, we may call the equilibrium position of these lines, i. e., the position which they would have in pure iron-carbon alloys if all

Jan 1, 1914

By Bauer, Alan

In considering blasting it is necessary to consider the drilling and explosives since one is generally concerned with the total cost of muck of a certain size in the pit or through the crusher. To get a current idea of the drilling situation in open pit mines plotted in Fig. 1 are the drilling costs per ton of material vs. hole diameter for rotary drill holes in large limestone, iron ore and taconite operations. The exception is the 2-in. diam hole which was drilled with a percussion drill in limestone.

Jan 1, 1968

By J. O. Mack, J. B. Russell

In recent years, solders containing 20 per cent tin with no bismuth or cadmium have been developed by a few companies, and personnel have been properly instructed in their use. In addition, since the tin shortage, a number of solders containing less than 10 per cent Sn, and some with no tin, are being used in special applications; however, a solder of this type has yet to be developed that is satisfactory for general use. Table i.—Composition Ranges Prescribed for a Commercial Substitute Solder Element Per Cent Tin............................ 18.0-20.0 Bismuth (maximum)a............ 0. 80 Silver.......................... O. 10-1. 25 Bismuth plus silver (minimum).... 0. 85 Antimony (maximum)............ o. 50 copper (maximum),,,,,,,,..,,,, 0. I3 Other elements, each (maximum)6 0.03 Lead........................... balance a When silver is present in excess of I per cent, the Bi content shall be 0.50 per cent or over. b Total not to exceed 0.10 per cent. The Purpose of this investigation was to develop an alloy containing a maximum of 15 per cent tin, with no cadmium or bismuth, having solder properties equivalent to or better than those of substitute solders now specified containing 18 to 20 per cent tin (Table I), or even approaching the properties of the standard 40 to 60 tin-lead solder. The wartime restriction of bismuth and cadmium, elements that have beneficial effects on fluidity, solidification range and strength, makes it increasingly difficult to develop a general-purpose solder containing a maximum of 15 per cent tin. In the course of this investigation, 11 elements were used in various combinations with the basic I5-85 tin-lead alloy. These elements were antimony, silver, copper, indium, thallium, lithium, calcium, barium, potassium, sodium and arsenic. In all, 116 low-tin solders were investigated, with the idea of developing a solder that will give satisfactory working properties, specifically in regard to "wetting" of copper, brass and iron, solidification range, capillarity and shear strength of a soldered joint. The relative importance of these various properties plays an important role in the search for substitute solders, since it is almost impossible to retain all of the desired qualities of a high-tin solder and still make drastic changes in the alloy composition. Because of the expected uses of a general-purpose solder, it is necessary that it have properties, especially in regard to wet-tability, that will enable it to be used on the metals in common use. Basic Considerations The maximum liquidus temperature of a solder is determined by the particular application involved and the temperature that can be obtained by the source of heat. If a soldering iron is used, it must not only

Jan 1, 1945

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By A. E. Bellis, T. W. Hardy

The problem of heat treating high-speed steel becomes more and more important as the design of cutters becomes more and more complicated in increasing the efficiency of mechanical operatioqs. Hundreds of dollars are spent in the design and manufacture of milling cutters of special form for rapid production of duplicate or interchangeable parts, and then, as the heat treatment is faulty on the one hand, or scientifically executed on the other, the tool fails after a few operations, or its efficiency is greatly increased. The practical operation of giving these complicated tools the right temperature necessary to bring out the best cutting qualities, and at the same time bring-the tool out "clean," is a difficult one and calls for no small amount of skill. In order to be on the safe side the average tool hardener uses a temperature much too low to give the best results with the high-speed steel he uses. In the case of cutters which are finished to a given diameter before hardening, it is impossible to grind the tool after hardening, so that it is essential that the surface be protected from oxidizing or de-carbonizing. It is the aim of this paper to describe some experiments on hardening high-speed stee1, in which metallographic means were used to determine the correct hardening tempcratures. The accompanying table and plates show the results of hardening experiments on five different high-speed steels. The analyses for carbon, tungsten, chromium and vanadium of each steel are given in the accom- . panying table. Six specimens from the same bar of each kind of steel

Jan 1, 1917

By Lillian Erskine

WHILE brass and other copper alloys have long been listed as offering health hazards to their workers, it is questionable if the metals involved are alone responsible for the trades' records of morbidity. The entire science of foundry sanitation is the product of the past two decades; and the best standards now operative would have been regarded as little short of revolutionary prior to 1910. The special handicap to the conservation of the health of the brass founder's employees has been the fact that, unlike the iron founder, his business could be profitably carried on in almost any small and unsanitary quarters. As a result, writers on occupational disease have accepted brass chills or brass founders' ague as an inevitable feature of the trade; and respiratory disabilities, as well as phthisis and disturbances of the nervous system, are also included as prevalent among those employed. While there can be no question as to the basic accuracy of past investigations, there is every reason to doubt the necessity for an undue percentage of ill health among brass molders and casters who are safeguarded by scientific ventilating standards and by improving personal habits of sobriety. There is, however, need for a campaign of education as to the most approved practices and equipment whereby the employer may safeguard the health of his workers, and thereby reduce his labor turnover and increase his productive efficiency. Broadly speaking, copper, tin, and aluminum carry negligible health hazards. The toxic qualities of lead, however, are a menace; especially if scrap lead is recovered or bought for foundry processes. The rapid volatilization of zinc renders its fumes and flocculent condensation the chief problems in conserving the health of the brass worker. The frequent presence in the foundry air of traces of arsenic compounds, lead

Jan 2, 1919

By Lillian Erskine

While brass and other copper alloys have long been listed as offering health hazards to their workers, it is questionable if the metals involved are alone responsible for the trades' records of morbidity. The entire science of foundry sanitation is the product of the past two decades; and the best standards now operative would have been regarded as little short of revolutionary prior to 1910. The special handicap to the conservation of the health of the brass founder's employees has been the fact that, unlike the iron founder, his business could be profitably carried on in almost any small and unsanitary quarters. As a result, writers on occupational disease have accepted brass chills or brass founders' ague as an inevitable feature of the trade; and respiratory disabilities, as well as phthisis and disturbances of the nervous system, are also included as prevalent among those employed. While there can be no question as to the basic accuracy of past investigations, there is every reason to doubt the necessity for an undue percentage of ill health among brass molders and casters who are safeguarded by scientific ventilating standards and by improving personal habits of sobriety. There is, however, need for a campaign of education as to the most approved practices and equipment whereby the employer may safeguard the health of his workers, and thereby reduce his labor turnover and increase his productive efficiency. Broadly speaking, copper, tin, and aluminum carry negligible health hazards. The toxic qualities of lead, however, are a menace; especially if scrap lead is recovered or bought for foundry processes. The rapid volatilization of zinc renders its fumes and flocculent condensation the chief problems in conserving the health of the brass worker. The frequent presence in the foundry air of traces of arsenic compounds, lead

Jan 1, 1919

By J. E. Harris

The metallic elements, beryllium, calcium, cerium, lithium, manganese, titanium, vanadium and zirconium are used in metallurgical practice in relatively small percentages for the purpose of improving the physical properties of various alloys. No important uses for any of these elements have thus far been developed either in the pure form or in alloys of which they constitute the major constituent.

Jan 1, 1935

By A. Moskowitz, L. S. Redmerski

The corrosion resistance of stainless steels can be strongly affected by surface treatments. Changes in corrosion resistance can relate to surface composition, integrity and stability of the passive film, and to surface profile (roughness). Operations producing oxidation at the surface, such as annealing, heat treating, and welding, can result in a chromium-rich scale and a chromium-depleted metal surface. In order to restore full corrosion resistance, chemical or mechanical clean-up techniques must remove not only the oxide, but also a very thin layer of metal. Laboratory and field test studies show that these factors are particularly significant in less highly alloyed steels. Annealing stainless in a reducing atmosphere (bright annealing) avoids chromium depletion, but as-bright-annealed material does not display optimum corrosion resistance in certain environments. Electro passiva-tion can be applied to improve pitting resistance without significantly changing bright surface appearance. Potentiometric studies show that electropassivated material also displays significantly greater resistance to breakdown of passivity in acid solutions. The application of special surface finishes for appearance purposes can affect corrosion resistance. Roughness is a key factor. Samples of related appearance but with different surface profiles can show significant differences in corrosion resistance. Thus nonreflec-tive stainless with a relatively smooth surface produced by a special rolling process is much superior to material chemically etched to a similar low reflectivity. THE corrosion resistance of a stainless steel is affected by other factors in addition to its bulk composition and metallurgical structure. These other factors include those relating to the specific chemical and physical condition of the steel's surface. This paper will consider certain aspects of surface condition in relation to corrosion resistance. In particular, studies will be described on the effects of oxidation encountered in heat treating or welding operations, of passivation after bright annealing, and of different surface finishes. EFFECTS DUE TO OXIDATION When stainless steels are exposed to high temperature in an oxidizing environment, as in annealing or welding, the oxides formed are relatively rich in chromium. As a consequence of oxidation, the metallic layer directly beneath the scale may be low in chromium to some very thin but finite depth.1"8 Such a change in chromium content could lower the corrosion resistance at the surface, whether or not the oxide layer is removed. Studies were performed relating to the effect of oxidation and chromium depletion produced during annealing and welding on the corrosion resistance of stainless steels. The nominal compositions of steels used in this study and others are given in Table I. A) Annealing Studies on 17 pet Cr Steels. 1) Effects of Pickling Treatments. Studies were performed to investigate the corrosion resistance of air annealed type 430 stainless as a function of the amount of electrolytic pickling after annealing. The material used in this study had been air annealed and electrolytically pickled in the mill. All scale had been removed, and yet the material showed unusually poor corrosion resistance. Laboratory electrolytic pickling studies were performed to determine whether additional metal removal from the surface would improve corrosion resistance. Electrolytic pickling was performed in a sulfuric acid bath using various conditions of bath acidity, temperature, time, and current density. The samples were then rated for corrosion resistance in a ferric chloride spot test. For this spot test, a solution was prepared by dissolving 10 g of FeCl3 . 6H2O, 5 g of NaCl, and 2.5 ml of concentrated HC1 in 200 ml of water. An area on a specimen was cleaned and a drop of test solution was placed on the prepared area. After 5 min, the drop was rinsed off and the area wiped dry. The spot was then rated between 1 and 5 by visual comparison with standard spots. The numerical rating of the standard spots can be described as follows: 1—No clouding of surface; 2—very slight clouding of surface; 3—slight clouding of surface; 4—moderate clouding of surface; 5—strong clouding of surface. A rating of 1 or 2 was considered to have passed the test, a rating of 4 or 5 represented failure, and a rating of 3 was considered borderline. The severity of etching in this test has been related to the actual chromium content at the surface.4 Etching (clouding) occurs on type 430 stainless (rating of 4 to 5) when the surface chromium content is 14 pct or less. The effects of current density and retention time when electrolytically repickling this material in 6 pct sulfuric acid are shown in Fig. 1. Increasing the cur-rent density or retention time improved corrosion resistance as measured by the spot test. Similarly, increasing acid concentration of the bath or bath tem-perature was found to improve corrosion resistance. The conditions making for improved spot ratings resulted in increased metal removal, regardless of specific pickling conditions used, Fig. 2.

Jan 1, 1970

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By Rufus J. Foster

During the discussion on the Preparation and Utilization of Sniall Sizes of Anthracite (page 613 of present volume), several inquiries were made concerning the use of the McClave grate, which was mentioned by Mr. Coxe as having proved satisfactory in the generation of steam at his collieries, and also at a large number of industrial estal)lishments in Scranton and elsewhere. For a more satisfactory repIy to such inquiries than could be furnished in the oral discussion, I have prepared the following paper to be included in the published proceedings. And, as the use of the fuel under consideration necessarily requires the employment of a blower to change the fire, from a condition giving an incandescent radiant heat only to one giving a hot gaseoua flame as well, I shall add a description of the McClave Argand blower and its method of action. The grate and blower combined form a complete and effective system fcr burning small fuels, such as anthracite culm, birdseye, buckwheat, bituminous slack, etc., in boiler and other furnaces; while the grate alone is now extensively used with the larger sizes of hard and soft coal in furnaces where blast is riot required. Fig. 1 is a view of the RlcClave grate as built in two sections. It is constructed on the principle best approved by practice to prevent warping and burning out; that is, it presents no long lines of

Jan 1, 1892