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By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study confirm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity. Three standardized combinations of Lake Superior brown iron ore with carbon were tested by similar procedures. One combination was a mechanical mixture of carefully sized high-temperature coke (1650°F) with the ore. The second was a mechanical mixture of the ore with Disco* obtained by carbonizing the identical coal at 950 °F. The third was an agglomerate prepared by carbonizing the coal and ore at 950°F, premixed in proportions to give as nearly as possible the same relative amounts of carbon and ore as the mechanical mixtures. This agglomerate, obtained by heating the finely divided ore (through 30 mesh) with coking coal through the plastic temperature range so as to form solid aggregates, gives a product in which the oxide particles are impregnated with, and intimately bound together with low-temperature coke. The agglomerate-—ore-Disco—was most active in oxide reduction; the mechanical mixtures of Disco and ore next in order, with coke the least reactive. General Discussion: Carbon exists in many forms and it is well known that the form or nature of the carbon used in reduction of oxides is related to the critical temperature of reduction. Sugar carbon, charcoal, and lampblack are forms of carbon that will reduce oxides at lower temperatures than high-temperature coke, and coke will, in turn, give a lower critical reduction temperature than graphite. There have been many investigations of this characteristic of carbons. Johnson' reported a difference of 130°F (70°C) in the critical reduction temperature of zinc oxide as between charcoal 1891 °F (1033°C) and Acheson graphite turnings 2021°F (1105°C) with zinc oxide. Bodenstein2 using charcoal and coke, found a difference of 138°F (77°C) comparing an experimental figure of 2066°F (1130°C) for coke and 1928°F (1053°C) for charcoal, in the reduction of zinc oxide. He concluded that this is very marked and observed that the "type of carbon merely raises or lowers the temperature at which rapid reaction takes place." Comparing the effectiveness of types of carbon in reduction of zinc oxide, it was found that a "brown coal coke" gave 97 pct zinc elimination at 1832°F (1000°C), as compared with 48 pct with "hard coal coke."' A wide range of metallic oxides was studied by Tammann and Sworykin,4 who found that the temperature at which decomposition of oxides begins depends on the nature of the carbon used. Carbon in the form of graphite, lampblack, and sugar carbon was investigated. Sugar charcoal will reduce Fe2O3 to Fe3O4 at 842°F (450°C) as compared with 1112°F (600°C) for coke, according to Meyer." Direct reduction of iron oxides by charcoal begins at 1382°F (750°C), but "first becomes intense" at 1652°F (900°C), whereas with coke, direct reduction begins at 1742°F (950°C), and "first becomes appreciable" at 2012°F (1100°C).6 he total reduction of the sample under certain conditions when heated in a current of CO with charcoal was about 100 pct for limonite and about 77 pct for magnetite. Using coke under the same conditions, the respective percentages were 75 and 47. In a study of processes for sponge iron7 by the Bureau of Mines, the conclusion was reached that a low-temperature char from noncoking subbituminous coal is the most satisfactory solid reducing agent. In a critical study of zinc smelting from a theoretical viewpoint Maier8 concluded that the reduction is by CO, that the reaction between ZnO and CO is intrinsically more rapid than the subsequent reduction of CO2 by C, which is limited by diffusion rates, which in part effectively limits the smelting process. Maier said that the operation is improved with the activity of the reducing carbon. An active carbon, he said, is one maintaining a low CO, content in the retort. Reactivity of Carbon: One form of carbon is more potent in reducing oxides than another. A carbon that reacts faster than another at a given temperature is said to be more reactive. Reactivity is measured by several methods, using carbon dioxide, air, or steam as reactants.9 ebastian and Mayers" have developed a method for the determination of absolute reaction rates between coke and oxygen by a study of ignition points under certain conditions. These and other investigators have established the relative reactivity of types of carbon. Lignite, charcoal, bituminous coal, cokes in the ascending order

Jan 1, 1951

By Finlayson J. F

The advantages of rapid and accurate analyses are becoming appreciated in many industries today and have resulted in a great increase in the number of samples received by their laboratories. This has caused some firms to consider the installation of one or more of the instruments available for analytical chemistry. In this country there are relatively few people with experience of instrumental methods and it is difficult for a firm considering the installation of such equipment to assess the advantages which instruments may give them, and to decide which instruments, if any, will be of most use to them. The object of this paper is to give a brief survey of instrumental methods in the field of inorganic analysis. Instrumental methods of analysis have numerous advantages when used correctly. They enable extremely rapid analyses to be made in many cases, e.g., analysis of refined lead by purely chemical means takes about two days whereas spectographically the analysis can be completed in approximately one and a half hours. The accuracy ofinstrumental methods, generally between 1 and 5%, is higher than most chemical methods for small percentages of impurities. Furthermore, if the instrument can be calibrated against absolute standards the errors are usually random and not biased to one side of the correct result. The sensitivity is high, enabling in many cases the detection and determination of smaller percentages than can be detected chemically. This high sensitivity enables and, in some cases, requires the use of very small samples, and results in considerable savings in reagents, allowing the analysis of considerably more samples without undue loss...

Jan 1, 1951

By D. E. Furman

The thermal coefficients of linear expansion for several stainless steels have been determined over the temperature range from —300° to 1000°F. The steels studied include types 301, 304, 316, 347, 310 and 330. This wide selection of compositions allows an insight into the effects of austenite stability and alloy content on the expansion characteristics. THE recent increased use of materials in low temperature applications has created a field for which the properties of austenitic iron, chromium, nickel alloys are particularly suited. Tensile and impact values of stainless steels at subzero temperatures have been made available in the technical literature but, as yet, little information has been published with respect to expansion characteristics. In order to supply this need, a study was made of several of the more common compositions. Those selected were types 301, 304, 316, 347, 310 and 330 stainless steel. Both the mean and instantaneous coefficients of linear expansion were determined over the temperature range from —300°F to 1000°F. Procedure The materials used were commercial grades with the exception of type 301 which was made in a 10# high frequency furnace. The compositions are listed in table I. All steels were given an anneal at 1950°F for 30 min and water quenched prior to machining the expansion specimens. Expansion readings were taken on specimens 0.250 in. in diam by 4.000 in. long with a fused quartz tube expansion apparatus similar to that described by Hidnert and Souder.1 Temperature measurements were made with a chromel-alurnel thermocouple calibrated for use at subzero temperatures. A bath of propane was used for temperatures from —300° to —100°F and one of alcohol from —100°F to room temperature. These baths were contained in large mouthed Dewar flasks and cooled to the desired temperature levels by passing liquid nitrogen through glass cooling coils placed in the flasks. The baths were stirred constantly for temperature equalization and were heated by immersing metal rods which were replaced frequently enough to give a heating rate of approximately 150°F per hr. A resistance wound furnace was used for heating from room temperature to 1000°F and throughout this range rates of about 450°F per hr were maintained. The furnace was designed so that the temperature gradient over the specimen was within 5°F. In most instances, the expansion readings were taken during heating from —300° to +300°F at

Jan 1, 1951

By C. G. Dunn, F. W. Daniels, M. J. Bolton

J. P. Nielsen—The data that Dr. Dunn and his associates have been obtaining are welcome checks on the theoretical aspects of grain boundary energies. With reference to the comments on the validity of the inter-facial tension concept, I should like to say that I have been having considerable difficulty myself in untangling the confusion between "interfacial tension" and "interfacial energy." The confusion however resolved itself for me when I learned that "interfacial tension" for solids, or at least crystals, is used with two distinct meanings. One meaning12. ' "hat is implied for "interfacial tension" is the work necessary to produce or increase the surface of the solid in question by a unit area, temperature and pressure held constant. This comes from the somewhat surprising but simple fact that surface tension and surface energy in the case of liquids are identical quantities. This synonymity has carried over to crystals, where it should be kept in mind that the tension connotation has meaning only by analogy with liquids and that no real stresses are being referred to. The only reason that there is apparently a set of stresses acting at a grain boundary junction is the optical illusion that liquid interfaces are being observed for the grain boundaries. The other meaning3,14,15 for the term has to do with actual states of stress in the surface of a material as would be measured by a system of forces applied to the surface to equate the surface stress state with that in the body of the crystal. J. B. Hess—Since the authors have proposed that the surface tension concept should be discarded in order to deal with the general case of interface energies in solids, their attention should be called to a recent paper by Gurney." The latter has shown, from a thermodynamic argument, that surface tension is a valid concept in solids. In fact, Gurney has rejected the idea that surface tensions are merely mathematical fiction and, instead, has given an interpretation of their physical reality. Finally, he has concluded that, as long as appreciable atomic migration takes place, specific surface energies and surface tensions must be equivalent in solids as well as in liquids. Accordingly, the authors' eqs 2 and 3 can be written with equal accuracy in terms of interface tensions, simply by replacing each E,! with its numerically and dimension-ally equivalent Interfacial tension ?,,. If the interfacial tensions (or specific energies) are independent of interfacial orientation, as is true in liquids, then the general equations that define the geometry at equilibrium of the common junction of three interfaces reduce to eq 1. However, neglect of the effect of boundary orientation is never completely justified theoretically' in dealing with crystalline solids; hence, use of eq 1 in such cases must always be considered as an approximation, though clearly a reasonable one for many purposes.1,2 At the same time, one should not be surprised that the assumption that interface tensions in solids are free from orientation

Jan 1, 1951

G. A. Moore—The tin-fusion method has been a very favorable possibility for many years. The authors apparently have settled the question that delayed the method for a long time by showing that no hydrogen is absorbed in the tin. This, of course, is very important. I want to make a few remarks concerning the absolute accuracy of analysis, which must be the final basis for deciding among the various methods. From the figures in the paper, there seems to be some re-maining slight discrepancy on the actual amount of hydrogen present in various samples which may be presumed essentially identical. (This is of the order of the precision of individual analyses but appears in averaged results.) From the analyst's viewpoint, the tally of hydrogen content can be regarded as occurring in three portions. First is a large portion which comes off easily and automatically during sample storage and later on heating in the apparatus. This is fairly easily analyzed. Second is an item which may be either positive or negative in the tally sheet. In warm or hot evolution, this is a portion which, in practice, can never be re-

Jan 1, 1951

By N. J. Grant, D. Carne, J. B. Seabrook

IT is unnecessary to review much of the literature on hydrogen embrittlement of steel since several excellent reviews and bibliographies exist.1-3 Hot acid pickling and cathodic charging have been known to cause hydrogen embrittlement of steel and have been used as laboratory methods to charge steels with hydrogen.4-8 Experimental Procedure The problem of prime concern in all instances, except in the work of Sims and coworkers,10 is that at no time was there a definite known hydrogen value reported which could be related to a particular value of the degree of embrittlement. It was the purpose of this research to determine the relationship between hydrogen content and degree of em-brittlement quantitatively. The 1020 stock used for the specimens was hot-rolled 7/16 in. diam rod of the following analysis: 0.19 pct C, 0.40 pct Mn, 0.012 pct P, 0.036 pct S' Vacuum-fusion analyses for nitrogen and oxygen gave 0.014 pct O2 and 0.0011 pct N2. Cathodic charging was used to cause embrittle-ment. The advantages of this method were that no quenching was necessary, the impregnation was reasonably controllable, and representative samples for analysis could be prepared simultaneously with the charging of the tensile bars. Analyses for hydrogen were made in a vacuum-fusion type of apparatus which extracted gas from the samples by fusion in a molten tin-iron bath' This apparatus, which has recently been described in detail elsewhere, will not be discussed here.". " Consecutive samples can be analyzed every 15 min with an accuracy of 0'03 ppm. A A from an electrolytic or pickling bath can be charged for analysis in about 3 min, and analysis completed in 15 min. Samples of as-received 1020 stock were analyzed and found to contain a negligible amount of hydrogen (0.06 ppm). Preliminary pickling and electrolytic charging gave highly variable results. Cold-worked samples showed higher values but ranged from 0.6 to 6.0 ppm of hydrogen. Charging at 90°C gave higher values of charged hydrogen, but troublesome films on many of the specimens resulted. It was not until a few drops of a catalytic poison, prepared from 2 g of yellow phosphorus dissolved in 40 ml of carbon disulphide,8 was added to the electrolytic cell that fairly consistent high values of hydrogen could be charged into the as-received 1020 steel at room temperature. The cell used is sketched in fig. 1. The anode and fixture for the tensile specimens were fastened to the cell cover as shown, and the specimen was screwed in place, centrally located with respect to the anode. At first, anodes of lead and graphite were tried, but they contaminated the electrolyte and gave a slight deposit on the specimen. Later, a platinum wire was used in the form of a uniform helix. A current of 2 amp, corresponding to about 0.5 amp per sq in. of cathode, was used for most specimens. The electrolyte was 4 pct H2SO4 solution. Fig. 1 shows the form of the special tensile bar, the main portion of which was an ordinary 1/4 in. diam, 1 in. gauge length test bar, except that two to four small cylinders of stock were left attached by small links to the bottom end of the tensile bar for the purpose of providing samples for hydrogen analysis. Thus the bars and samples were charged with hydrogen simultaneously and an analysis could be made while the bar was being tested mechanically. Experiments were performed to determine how representative the test cylinders were of the middle of the test bar proper. While the bar center was being analyzed, the small cylinder was stored in dry ice, since it had been shown that such storage prevents loss of hydrogen for many hours.12 The results of these checks are shown in table 1. The checks are very good (0.3 ppm) and indicate that it is permissible to use the small end cylinders to establish the hydrogen content of the tensile test bar proper-

Jan 1, 1951

By B. M. Larsen, T. E. Brower, J. W. Bain

A mass of circumstantial evidence is presented to indicate that the main source of alloy losses in open-hearth tapping is oxidation by air, with the steel apparently reacting with an amount of oxygen equivalent to about 30 times its own volume of air. The effect is erratic from heat to heat, depending largely on turbulence and distance of free fall of the stream of liquid metal. THIS paper reports another phase in a general study of oxidation in the open-hearth, various aspects of which have already been discussed in previous papers.1,2,3 It is based on experiments conducted on commercial, basic open-hearth furnaces at various times when opportunity offered, beginning about 1938, in an attempt to determine the mechanism and measure the amount of air oxidation during the flow of the tapping stream through the air into a ladle. This effect is closely connected, not only with alloy losses and control of chemical analysis, but possibly with various questions regarding inclusion content and steel quality and with a true picture of the deoxidation of steel in general. Thus it is believed that discussion of a large part of the results to date may be of assistance to others who are studying problems related to deoxidation or to steel cleanliness and quality. The literature reveals that strangely little attention has been devoted specifically to the effect of pouring steel through open air. Bardenheuer and Henke4 in 1939, in a paper devoted largely to overall losses of manganese in the basic open-hearth, reported that for a number of heats tapped into a tilted ladle held just beneath the runner so that the maximum distance of drop of the stream through the air was held to less than about 30 in., there was in most cases almost no loss of manganese from furnace to ladle. Hultgren,5 in 1945, showed that in high-carbon basic electric steel deoxidized in the furnace and containing no large inclusions as it left the furnace, large silicate inclusions, often rich in manganese oxide, were present in samples dipped from the pool in the ladle; also that the rise in content of large inclusions (above 0.01 mm dim) was greater when the metal stream was made to spray or flow in a turbulent manner. Our interest in this phase of oxidation in the open-hearth was first aroused by a study of alloy efficiencies on ladle additions. The frequency curves of manganese efficiency (net recovery of metal added in ladle) given in fig. 1 are of interest in this connection. Lowest, and also most variable (47 to 95 pct), recovery was in low-carbon heats having no coal additions to the ladle, progressing upward to a maximum average and least variable (82 to 97 pct) recovery in high-carbon heats killed with aluminum and silicon. Both coal additions and higher carbon contents in the tap stream, as well as additions of silicon and aluminum, help to lower the amount of manganese loss. But the most interesting point is the amount of manganese oxidized in many heats tapped at 0.50 to 1.06 pct carbon. It has been shown in a previous paper3 that the amount of oxygen in the tap stream in such heats is very small, usually below 0.01 pct, too small to oxidize any appreciable amount of manganese. Also, the fact that manganese should be oxidized at all in a metal solution containing such more stable oxide-forming elements as aluminum and silicon is an indication of some rather intense oxidizing effect such as could be caused by reaction with the air during ladle filling. Oxygen Balances from Tap Stream to Teeming Stream: Data in the form of alloy efficiencies, such as those shown in fig. 1, are not a proper measure of such a general oxidation effect. Having available

Jan 1, 1951

By M. G. Driessen, H. E. Criner

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D ,41 Elimination efficiency, in the terminology of Dahl-strom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By R. C. Buehl, J. P. Morris

F. D. Richardson—The authors are to be congratulated on this further contribution to our knowledge of the thermodynamics of the interaction between sulphur and carbon and silicon in liquid iron. As the authors state, the influence of carbon and silicon on the activity coefficient of sulphur in liquid iron is clearly of great importance in the blast furnace, since it must cause a three to fourfold improvement in the partition of sulphur between slag and metal. The influence of increasing temperature in further increasing the activity coefficient of the sulphur in the metal in the blast furnace by increasing the carbon content is also of interest. This effect, however, is probably only part of the reason for the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing temperature. Other contributing factors are the lowering of the oxygen potential in the presence of carbon by increasing temperature and the probable increase in the activity coefficient of the lime in the slag for the same reason. The former of these effects, which works via the (CaO) + [S] = (CaS) + [O] equilibrium, might possibly account for a 70 pct improvement in the sulphur partition and the latter might give a further 50 pct improvement. C. Sherman—I would like to compliment the authors on their very careful research. If I may, I would like to show results of calculations on the carbon-sulphur-iron system similar to the ones that were shown in our paper for the silicon-sulphur-iron system. For Fe-S-C ternary system k=PHgs/PH2 x 1/(f1°) (f2°) (%S) where fs = sulphur activity coefficient fs' = fs for Fe-S system of equal pct S f3° = f2/f2 for Fe-S-C ternary system This same analysis has been used on other systems, but the results shown in fie.- 7 are for carbon and silicon. L. S. Darken—I would like to make two brief comments in addition to complimenting the authors on an apparently very precise and accurate investigation. The first is that the present work is in agreement with a calculation by Larsen and myself." Our calculation (much less precise than the present work) was based on: (1) Unpublished work on the sulphur content of molten iron (1.5 pct at 1500°C) in equilibrium with graphite and an iron sulphide slag; (2) the distribution coefficient of sulphur between slag and carbon-free liquid iron. We expressed the result in a form equivalent to log 7. = 0.18 [%C] which gives an activity coefficient (?s.) of sulphur only slightly higher than the authors find and certainly within the precision of the earlier work. My second comment concerns the correlation of the thermodynamic findings with atomistics. A rough pic- ture of the atomic arrangement in the liquid solution is rather easily conceived for this particular liquid solution containing iron, carbon, and sulphur. Carbon has a very much stronger affinity for iron than for sulphur. Hence we may conclude that a sulphur atom will but seldom be adjacent to a carbon atom—since this would be a position of high energy. From the metallic radii of iron and carbon we know that six iron atoms pack neatly around one carbon atom. Thus each carbon atom in retaining this shell of iron atoms (which latter may not be replaced by sulphur on account of the high energy requirement) decreases the available positions for each sulphur atom by six. Hence each atomic percent of carbon decreases the equilibrium sulphur content by 6 pct (of itself). Or, at low concentration each atomic percent of carbon increases the activity coefficient of sulphur by 6 pct. This is in good agreement with the observed increase (6 or 7 pct at low carbon content). It is indeed gratifying to find a case where, by such simple reasoning, quantitative agreement is found between precise data and the modern picture of the atomistics of the metallic state. J. P. Morris (authors' reply)—We would like to point out that there is an error in the equation on p. 322 of the paper. The third equation should read: ½S2 (gas) + H2 (gas) = H2S (gas) The authors wish to thank everyone for the interest they have shown in the paper. In regard to the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing the temperature, Dr. Richardson is correct in stating that the cause can be attributed only in part to the increase in activity coefficient of sulphur resulting from the rise in carbon plus silicon content of the metal with rise in temperature. However, this factor is probably an important one. The results of one experiment, performed since this report was written, indicate that at a constant temperature the addition of silicon to a melt saturated with carbon causes an increase in the activity coefficient of sulphur even though the carbon solubility is lowered. In this test, 2.5 pct silicon was added to a melt saturated with carbon and maintained at 1400°C. Although the carbon content dropped from 4.85 to 4.1 pct, the activity coefficient of sulphur was increased by about 20 pct.

Jan 1, 1951

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson's paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence' but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

By D. E. Norquist, J. E. Moeller

The results of wear on marked balls, 4, 31/2, 3, and 2 in. diam are given. All balls were forged steel of practically the same chemical analysis and hardness. The results indicate that balls in a given mill for a given length of time will have equal diameter losses, regardless of size. IN order to determine the relative wear rates of several sizes of grinding balls, groups of 4, 31/2, 3, and 2 in. balls were marked individually and were charged, all at the same time, into each of two production mills grinding copper ore. The remainder, and vast majority, of the ball charge consisted of 2 in. diam, and smaller, white, cast iron balls. The original weight of each test ball was determined and recorded. Some of each group of test balls were recovered from the mills periodically, individually reidentified, and reweighed. The test balls were recovered during regular maintenance shutdowns, at approximately thirty-day intervals, so as to avoid disrupting operations. As soon as the weights had been recorded, each marked ball was recharged into the mill from which it had been taken. The test units were mechanically the same and theoretically received equal tonnages of feed. All of the test balls were of forged, alloy steel composition with only slight variations in chemistry that would not be expected to affect the physical properties. All were heat treated in the same manner to produce a high hardness, as equal as possible for all sizes and as uniform as possible from surface to center. Generally speaking, the hardness of the portion worn from the balls during the test ranged from 62 to 65 Rockwell C. The microstructure was, therefore, predominately martensitic. The method of marking the test balls consisted of forming a small, round hole, 3/16 or 1/4 in. diam, into the center of each test ball with a Thomas Metal Master disintegrator, which produces a hole in fully hardened steel without affecting the hardness of the surrounding metal. After the hole was formed, each test ball was individually weighed to the nearest gram and the weight was recorded. The balls were grouped as to size and each group assigned a code letter. The individual balls within the various groups were then assigned a number. A small copper disc was stenciled on one side with the group letter and on the other side with the individual ball number and dropped into the hole in the corresponding test ball. The hole was then plugged with a low-melting-point metal alloy, which could be melted out in boiling water. Half of the test balls in each group were charged into one mill and the other half into another mill, so that all test balls in each mill would be subject to, as nearly as possible, identical conditions for an equal length of time. Previous testing had indicated that the wear rates on balls of different sizes could not be accurately compared if weight loss, or percentage weight loss, were used as a basis for comparison. Fig. 1 is a graphic record of the average weight loss for each size group in mill No. 1, and it becomes readily apparent that the larger balls lose substantially more weight in a given length of time. Fig. 2 is a graphic record of the average percentage weight loss for each size group in mill No. 1, illustrating that the smaller balls definitely lose a greater percentage of their original weight in a given length of time. It was, therefore, decided to convert the actual weights of the test balls to diameter and follow the diameter losses periodically to see if the wear rates

Jan 1, 1951

Jan 1, 1951

By E. E. Donath, W. L. Crentz, D. Doherty

IN 1948, the United States used nearly six million barrels of petroleum products every day. Although substitution of synthetic fuels for the natural petroleum product is not here yet, large quantities of special-purpose coal will be required in ever-increasing volume as the domestic production of oil from other sources fails to meet demand and the production of synthetic fuels begins. Petroleum economists do not agree as to when the shortages of domestic oil will appear; but the increasing per capita consumption of oil, coupled with a constantly growing population drawing on a potential domestic oil supply estimated to be 85 billion barrels, sooner or later will result in demand exceeding domestic supply. When this situation comes about, the excess demand will be either eliminated by curtailment of consumption or the demand met by increasing importation of foreign oil or by the production of synthetic fuels. The first recourse would definitely retard the heretofore unbroken rise in American living standards, while dependence upon a foreign oil supply during a war or other emergency would be dangerous. On the other hand, the enormous coal reserves in the United States, plus sizable deposits of oil shale, indicate adequate means of augmenting a diminishing domestic oil supply. Some idea of the impact of an expanding synthetic liquid fuels program on the coal-mining industry may be gathered when it is considered that to supply just half of our present-day petroleum needs synthetically from coal would increase the coal output by about 500 million tons annually, using an 11,900 Btu bituminous coal as the plant feed. If either a subbituminous coal or lignite were used, the quantity required would be materially increased. Synthetic Fuel Processes: The principal synthetic fuel processes using coal as a raw material are the Bergius, or coal-hydrogenation process, and the Fischer-Tropsch, or gas-synthesis process. These two processes not only produce different end products, but the preparation of the coal used in each presents its own individual problem to the coal-preparation engineer. The hydrogenation process brings together a mixture of dry, finely powdered coal, catalyst, and heavy oil to form a paste. Addition of hydrogen under rather high pressure and temperature conditions brings about transformation of the coal to a liquid product, from which a high-grade gasoline and other motor fuels may be obtained. The Fischer-Tropsch process requires the production of synthesis gas, a mixture of carbon monoxide and hydrogen. At the Bureau of Mines Louisiana, Mo., demonstration plant, this gas is being made by reacting dried pulverized coal with carefully controlled volumes of oxygen and superheated steam. After purification and in the presence of the proper catalyst and suitable conditions of pressure and temperature, the hydrogen and carbon monoxide components of the synthesis gas react to form motor fuel. The two processes are not competitive but rather com-

Jan 1, 1951

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

The editorial expenses for the preparation of the manuscript of the second edition, as for the first, were provided by grants of the Engineering Foundation and the Open Hearth Steel Committee of the Iron and Steel Division, AIME ; the Seeley W. Mudd Memorial Fund again sponsored the publication of this volume. The companies and research or educational institutions with which the authors, reviewers, and editors are connected also contributed much to the writing and editing of this book through their generous donations of time and travel and office expenses. And finally, the authors and others have given countless hours of their own time with no recompense but the satisfaction of a job well done. In order to give credit to the companies or educational institutions which made it possible for the members of the Editorial Board to devote considerable time to the revision of this book, the names of these members and their affiliations are recorded here as follows W. O. Philbrook, Carnegie Institute of Technology M. B. Bever, Massachusetts Institute of Technology H. B. Emerick, Jones and Laughlin Steel Corporation B. M. Larsen, United States Steel Company A number of individuals suggested desirable changes in the book before rewriting was started. Almost all manuscripts were gone over critically by reviewers, and the resulting criticisms led to the correction of errors and omissions and greatly contributed to the accuracy and completeness of the text. Other people have supplied additional data or illustrations or assisted in other ways. While some of these contributors must remain anonymous because they are not known to the Editors, the cooperation of the following individuals is gratefully acknowledged: R. D. Allen, Republic Steel Corporation, Chicago Isadore Amdur, Massachusetts Institute of Technology Mary Baeyertz, Armour Research Foundation S. P. Bahmer, Republic Steel Corporation, Massillon E. C. Bain and Associates, United States Steel Company, Pittsburgh C. W. Briggs, Steel Founders' Society of America H. W. Briske, Wisconsin Steel Works

Jan 1, 1951

By W. G. Woolf, A. Y. Bethune

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process' for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt's earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.'s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

The United States has not begun commercial operations to tap its largest poten-tial sources of oil supply - oil shale and coal. The reason is that domestic petrol-eum has been plentiful in the past and liquid products probably could be produced from it at the lowest cost. In view of the ever-increasing need for petroleum in the United States, the critical international situation threatening foreign supplies, the growing demands for steel, and the heavy costs to industry of constantly discovering and developing new oil fields, it is believed that the prompt development of a synthetic fuel industry based on oil shale and coal is not only requisite to safeguard our oil supply but is an economically sound course for the foreseeable future, To neglect its development is to close our eyes and minds to our own resources at a time when they are needed critically. It also is apparent now that neither the Government nor industry would be taking any considerable economic risk in starting the initial plants, especially as measured against their potential value in meeting critical oil and chemical demands and in building a new industry in the West.

Jan 1, 1951

By C. A. Wert

THE solid solubility of cementite in a-iron has been investigated a number of times and there is now general agreement on the solubility of about 0.018 wt pct at the eutectoid temperature, 720°C. With decreasing temperature, the solubility falls off so rapidly and to such a low value that no data obtained by standard metallurgical methods are available below 500°C. Using a new technique, however, Dijkstral has obtained apparently accurate solubilities down to 400°C; which data agree well with previously measured solubilities in the 600" to 700°C temperature range.' The present paper has in part the purpose of extending his work to still lower temperatures. Earlier work of Low and Gensamer3 on iron has established that the presence of a relatively small amount of carbon can play a tremendous role in affecting the mechanical properties. In particular they found that the yield point remained high as they reduced the amount of carbon in the iron; the yield point dropped only after the carbon content had fallen to something less than 0.003 wt pct, the point where their carbon analysis failed. It seemed desirable to the present author to see if some means could not be found to extend this part of their work. This investigation has then the additional purpose to determine the range of carbon concentration in which the major change occurs. Solubility The method used in the present work to measure small percentages of carbon in a-iron utilizes internal friction. Since this method may not be fa-miliar to the reader, the following explanation will be given (a part of this procedure is from unpublished results of Dijkstra): It is known that the internal friction associated with the diffusion of

Jan 1, 1951

IN the preceding chapter on thermochemistry and the reactions in and between metal and slag phases and in the following chapter on fuel combustion the main emphasis is placed on the equilibrium or "static" conditions. This equilibrium viewpoint is not concerned with the rate of change in the process or with the mechanisms or paths followed between initial and final states. The questions of just "how it works" and "how fast" belong to the kinetic aspect of any process; their answers are helpful in speeding up or slowing down and thus controlling its operation, and also in understanding its limitations. Any treatment of kinetic factors in the open hearth such as is attempted here and in Chapter 22 must at present be largely qualitative and incomplete. We are only beginning to get quantitative data on rates of reaction and diffusion at high temperatures, as indicated in Chapter 15. Empirical data in the literature on furnace operating rates do not help much to illuminate the details of gas-flow patterns and the complexities of heat flow in the many parts of the furnace system. This chapter is intended to give the reader an introduction to the problems of the flow of gases through the furnace system and the flow of heat in this system. An adequate discussion would require several times the space available here; it is possible here only to outline a few fundamentals and to indicate some of the conditions of heat and gas flow peculiar to the open hearth. Several good general treatments of these subjects may be found in the literature (see references at the end of the chapter). For the designer of open-hearth furnaces, the principles of gas flow are of paramount importance. They are also important to the operation of the process, at least to the extent of a general qualitative picture of the movement of gases in the system. MOTION OF GASES IN FURNACE DUCTS Fluid flow in general can vary between the extremes of laminar or streamline flow with a minimum energy loss, to irregular

Jan 1, 1951

By K. C. Dean

During investigation of the occurrence of manganese deposits in the western United States, examining engineers of the Bureau of Mines collected samples from several properties in Montana. Extensive laboratory tests were made to determine the amenability of these ores to standard ore-dressing methods of concentration to produce marketable-grade products. The Tzarena claim, one of the properties sampled, is on the western end of the Rama or Black Chief vein in the city of Butte, Silver Bow County, Mont., on the southwestern periphery of the mining district. The Black Chief 'WAR system contains one of the largest and most extensive known rhodochrosite deposits in the world. Test work was conducted on two samples of Tzarena ore. Sample 1 is representative of a vain 5 feet wide on the 150-foot level of the Tzarena shaft. Sample 2 is representative of a vein 8 feet wide in the 100-foot level of the shaft. The Minnie Jane mine, 1/2 mile northwest of the Tzarena claim, contains ore similar in mineralogical composition to Tzarena ore but differing materially in manganese content and to some extent in physical characteristics. Ore-dressing investigations were made on three samples of Minnie Jane ore. Sample 1 represented stock-piled ore, sample 2 represented ore from Minnie Jane mine having a considerable sulfide content, and sample 3 represented low-grade ore.

Jan 1, 1951