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By R. Q. Shotts

Nitric acid oxidation rate analyses of three coals, previously studied microscopically by the Bureau of Mines, revealed three components. Relative quantities agree with those found for the four components given by the Bureau and results are consistent with current ideas of coal constitution. Possible multi-component composition for bright coal and a reactivity-rank relation are suggested. THE physically dissimilar components of bituminous coals often are easily recognized mega-scopically. Under the microscope, reflected light or light transmitted through thin sections reveals the presence of the different components, even when these are intimately mixed. Optical methods for the quantitative estimation of the relative abundance of the various components, both by means of thin sections and by particle count, have been fully described.'. ' It has long been recognized that there are chemical and physical differences between the various petro-graphic components of bituminous coals, although analytical differences usually are small.:'. ' Only in the case of fusain have chemical differences been used for quantitative determination of a component. C. C. Hsiao and associates, at the Mineral Industries Experiment Station of the Pennsylvania State College, have described a method of analysis which is based upon the differences in the rate of nitric acid (8N) oxidation, fusain, and the other components of coal."," The reproducibility of their method and its applicability in checking microscopic determinations of fusain content have been supported by several independent investigations.'. " The writer has proposed the use of differences in oxidizability for the estimation of other components." "' The results of the oxidation of whole coals and of float-and-sink fractions of coals were reported. In most cases the plots of the logarithms of the percent dry, non-fusain, organic residue from oxidation, against time, revealed the presence of at least two distinct components. Both components appeared to oxidize according to a first order law, but the reaction constants for the components were distinctly different. One or more of the dull density fractions were found to contain but one component, and some of the lower rank coals oxidized in such a way as to suggest the presence of three components. A suitable way to check the identity and significance of the components delineated by oxidation would be to analyze a sample of coal both by the nitric acid oxidation procedure and by a microscopic method. The writer was wholly unfamiliar with either of the microscopic techniques commonly used, and to make such a comparison it was necessary to rely upon microscopic analyses made by someone else. It is hoped that some laboratory which is equipped to make both types of analyses will some day make them upon identical samples. During the past 20 years, four Alabama coals have been analyzed petrographically and the results published by the United States Bureau of Mines. They are: 1—Flat Top mine, Mary Lee bed; 2—Empire mine, Black Creek bed; 3—Wylam No. 8 mine, Pratt bed, all in the Warrior field; and 4—Soot Creek mine, Fairview bed, in the Coosa field."-" Of these, only the Flat Top mine is still operating. Because of the closing of these mines, it first appeared necessary to rely upon the indirect and unsatisfactory procedure of sampling the beds in other mines located as near to the closed mines as possible. Upon investigation, however, it was found that the Bureau of Mines still had, in storage, the very same samples which had been used in the published petrographic studies. The Bureau very generously furnished about 2000 g each of the Pratt, Mary Lee, and Fairview bed coals, largely lumps but with some fines. The blocks of coal, when received, still were covered by the paraffin coating which had been placed on the polished surface, in the case of the Mary Lee coal almost twenty years ago. Procedure The procedure for oxidizing the coal sample and removing the alkali-soluble humic acid has been described. In the present study, oxidation periods of 1/6, 1/3, 1/2, 3/4, 1, 2, 3, and 4 hr were used. All oxidations were made in triplicate. After the paraffin had been removed in boiling water and the coal washed carefully with cold benzene, the entire sample of approximately 2000 g, obtained from the Bureau of Mines, was crushed to pass a No. 4 sieve. About 200 g of this material was pulverized to pass

Jan 1, 1954

By T. W. Watson, D. R. Flynn

Measurements have been made of the thermal conductivity and electrical resistivity of two specimens of 0.005-cm (2-mil) Be-Cufoil over the temperature range -140° to +200°C. The thermal cmductivity of Be-Cu Alloy 125 was found to be significantly higher than that of Alloy 25, which had a higher impurity content. The thermal conductivity and electrical resistivity values obtained were in concordance with the Smith and Palmer relation for copper alloys which states that ? = 0.0239 (T/p) + 0.075 where A is thermal conductivity (W cm-' deg-'), p is electrical resistivity (microhm-cm), and T is absolute temperature (OK) , indicating that the Smith and Palmer relation can be used to predict the thermal conductivity of this type of Be-Cu alloy over the temperature range -140" to + 200°C to within an accuracy suitable for most engineering applications. THE National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, Md., requested the National Bureau of Standards to measure the thermal conductivity of 0.005-cm Be-Cu foil which was to be used to fabricate antennae for use in Radio Astronomy Explorer space craft. It was felt that measurements had to be made on the actual antenna material, rather than on a thick bar of similar material, since the cold-working and age-hardening properties of the alloy would make it very difficult, if not impossible, to place a thick bar in the same metallurgical state as the 0.005-cm material. As discussed in Section 111 of this paper, the thermal conductivity of many copper alloys can be computed rather accurately from electrical resistivity data using an empirical relation developed by Smith and palmer' and further confirmed by owell.' However, there has been very little work done on correlating thermal and electrical conductivities on Be-Cu alloys. We were reluctant to assume the validity of the Smith-Palmer relation on Be-Cu alloys because of the very large mass difference between beryllium and copper. As will be seen, however, our experimental results indicate that the Smith-Palmer relation is valid for the two alloys on which we made measurements. I) DESCRIPTION OF SAMPLES Samples of Be-Cu Alloy 25 and Be-Cu Alloy 125 were furnished to NBS in the form of rolled strip material, 0.005 cm thick by 5.08 cm wide. The Be-Cu Alloy 25 was purchased by NBS in the form of a continuous length of flat strip. The Be-Cu Alloy 125 was furnished to NBS by Goddard Space Flight Center in the form of two lengths of strip that had been formed into "tubing" of about 1.2 cm diam, with one side of the strip overlapping (but not connected to) the other side by about 90 deg. This "tubing" had been opened up to be flat and then rolled onto spools of about 3 cm diam. When unrolled, the strip would spring back into tubular form. Samples of both of the Be-Cu alloys were chemically analyzed by the NBS Analytical Chemistry Division. The beryllium content was determined quantitatively by the phosphate-gravimetric method to be 1.83 wt pct for Alloy 25 and 1.80 wt pct for Alloy 125. The two alloys were also examined by a general qualitative spectrochemical method for metallic elements. The Alloy 25 specimen contained between 0.1 and 1.0 wt pct Al, Co, Fe, and Si and between 0.01 and 0.1 pct Ni. The Alloy 125 specimen contained between 0.1 and 1.0 pct Co and between 0.01 and 0.1 pct Al, Fe, and Si. Other metallic elements present were in amounts less than 0.01 pct. The NBS Engineering Metallurgy Section measured the tensile strength, elongation, and Knoop hardness of both the Be-Cu Alloy 25 and the Be-Cu Alloy 125. These are given in Table I. The NBS Engineering Metallurgy Section also prepared photomicrographs of the two alloys; these are shown in Figs. 1 and 2.

Jan 1, 1969

By William Fink

THE investigation of the phase relations of high-purity aluminum-base alloys is a part of the fundamental research program of the laboratories of the Aluminum Company of America. The results of a number of binary and ternary systems have previously been published in the transactions of this society. The aluminum end of the binary aluminum-titanium system has been studied. This system has received relatively little attention. To the authors' knowledge, there are two previous papers on this subject. E. van Erckelens1 determined the constitutional diagram reproduced in Fig. 1. .According, to this diagram, the liquids represents the separation of TiAl4 (Ti = 30.7 per cent.). He concluded that this is the composition of the compound, because in his work the eutectic horizontal terminated at 30.7 per cent. titanium and the metallographic examination of a sample of this composition revealed only one phase. According to the constitutional diagram developed by W. Manchot and A. Leber,2 reproduced in Fig. 2 from data given in their article, the liquidus represents the separation of the compound TiAl3 (Ti = 37.2 per cent. ). The composition of the compound was derived in a manner similar to that utilized by van Erckelens. Moreover, Manchot and Leber confirmed the composition of the compound by analysis of the constituent left as a residue after dissolving the alloys in weak sodium hydroxide solution. Although these are the only publications describing the constitution of the system, other investigators have studied the composition of the titanium compound. L. Wöhler3 says that there is a compound TiAl3 which was later confirmed by W. Manchot and P. Richter4 and by

Jan 1, 1931

By R. D. Stover, F. O. Shuck

The variation of binary-diffusion coefficients with composition in the liquid Bi-Sn system at 300°C was measured using the capillary-reservoir technique. The experimental coefficients did not exhibit a simple composition dependence. A number of tests were also made to determine the effect of variation of density with composition on convection within the capillaries. These tests indicate that the density changes arising from composition duferences may give rise to high diffusion coefficients unless care is taken to maintain a stable configuration. In recent years there has been considerable interest in diffusion in liquid metals. However, the bulk of the work done to date has involved measurements of self-diffusion or diffusion of dilute concentrations of "solute" metals. Because there are possible applications to liquid phase processing of metal alloys and since additional data may help to clarify the nature of diffusion in liquid metals, investigations of the concentration variation of diffusion coefficients in binary alloys have been undertaken. Of past studies only two have covered large ranges of binary composition. Niwa et al.' investigated the Pb-Sn, Bi-Pb, and Bi-Sn systems and Grace and Derge2 investigated the Bi-Pb system. Because of the discrepancy between the data of these investigators, it was deemed desirable to check the possibility of convection arising from the variation of density with composition. The capillary-reservoir technique of Anderson and saddington3 was chosen for the present investigation since it has been widely used for measurements involving dilute solute concentrations and it was the technique used by Grace and Derge.2 It was necessary, however, to modify the normal procedure of using a pure metal bath to avoid measurement of integral diffusion coefficients over large concentration ranges. The alloy system chosen for study was the Bi-Sn system for which there are some data available.' EXPERIMENTAL PROCEDURE In order to utilize the capillary-reservoir technique for measurements of diffusion coefficients as a function of composition, it was necessary to modify the normal procedure slightly. This modification consisted of using a reservoir composition which was only slightly different from that in the set of capillaries, in order that the integral coefficients measured might be taken over a small composition range and might thereby be assumed to approximate the differential coefficient at some average composition between that of the capillary and that of the bath. It was found that a composition difference of approximately 0.10 mass fraction provided a satisfactory compromise between a small increment in composition and reasonable accuracy in measuring changes of composition. The alloys were prepared from tin and bismuth of 99.999 pct purity. The materials were first cleaned of surface oxides, then weighed and melted to form a homogeneous alloy in a Pyrex filling apparatus. The capillaries used were of precision bore Pyrex tubing 1.000 *0.005 mm bore. Capillaries of various lengths (from 2.85 to 5.85 cm) were cut and sealed at one end by fusing a 3-mm Pyrex rod to the end. The capillaries were filled by inserting them into the filling chamber, evacuating the chamber, submerging the capillaries, and pressurizing the chamber with argon. Two sets of capillaries were prepared for each run. One set contained an alloy more dense than the bath alloy and one set a less dense alloy. This procedure was followed so that the effect of density difference on the measurement could be determined. After filling one set of capillaries, these were placed open end up in a capillary holder and transferred to the diffusion chamber which consisted of a Pyrex tube inserted into a graphite block. The second set of capillaries was then filled and placed into the diffusion chamber. The reservoir alloy, which had been melted in a separate crucible, then was poured carefully into the diffusion chamber. Sufficient reservoir alloy was used to cover all capillaries to a depth of several centimeters. All of these operations: capillary filling, melting of alloys, and diffusion anneal, were carried out in a fused-salt bath which maintained a temperature of 300"*1°C. All capillaries were permitted to diffuse for approximately 48 hr. At the end of the diffusion period the capillary holder was removed from the bath and

Jan 1, 1969

By R. J. Jackson, D. E. Williams, W. L. Larsen

The phase diagram of the Ta-Zr system is presented with a discussion of the methods used in its determination. The solidus contains a minimum at 1820°C near 25 wt pet Ta. A complete solid solution exists at elevated temperatures between tantalum and ß zirconium. This solid solution decomposes monotectoidally at 800°C and 12 wt pet Ta. The maximum solubility of tantalum in a zirconium is slightly less than 2 wt pet, and decreases with decreasing temperature. The solubility of zirconium in tantalum is 5 wt pet at the monotectoid temperature and about 2 wt pet at room temperature. THIS investigation was part of a program of research on refractory metal alloy systems having potential application in nuclear reactor technology. Preliminary prop-ess has been reported in the Ames Laboratory annual research reports.l Most of the previously reported work on the Ta-Zr alloy system consisted of partial phase diagram investigations and the determination of the mechanical properties of the zirconium-rich alloys. Anderson eta1.2 studied alloys containing up to 30 wt pet Ta as part of an investigation of several zirconium alloy systems. These investigators also determined some of the mechanical properties of the alloys at room temperature and 650°C. In a discussion of Anderson's work, Pfei13 suggested that the bright phase in the microstructures of the intermediate alloys is a tantalum-rich solid solution or an intermediate phase in a matrix of ß zirconium solid solution. Litton,4 Keeler,5 and Chubb6 determined the mechanical properties of zirconium-rich alloys at ambient and elevated temperatures. Van Thyne and McPherson7 reported the tensile properties

Jan 1, 1962

By Paul Billingsley, Augustus Locke

The mining districts of the first order' of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of compressive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 Nature of the Thrust Arc The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The. cross-sections are as shown in Fig. 2. The backbone of the belt is the upward and eastward moving block represented by the Glacier Park, the Wasatch, and the Virgin mountains, successively. The structure represented on these sections is the culmination of events which began far back in geologic time and throughout which a contrast has existed between the regions east and west of the backbone line. Before the Pennsylvanian, as Fig. 3 shows, there was a shallow shelf on the east and a deep marine trough on the west; after

Jan 1, 1935

By Paul Billingsley, Augustus Locke

The mining districts of the first order' of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of compressive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 Nature of the Thrust Arc The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The. cross-sections are as shown in Fig. 2. The backbone of the belt is the upward and eastward moving block represented by the Glacier Park, the Wasatch, and the Virgin mountains, successively. The structure represented on these sections is the culmination of events which began far back in geologic time and throughout which a contrast has existed between the regions east and west of the backbone line. Before the Pennsylvanian, as Fig. 3 shows, there was a shallow shelf on the east and a deep marine trough on the west; after

Jan 1, 1935

The mining districts of the first order' of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of compressive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 Nature of the Thrust Arc The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The. cross-sections are as shown in Fig. 2. The backbone of the belt is the upward and eastward moving block represented by the Glacier Park, the Wasatch, and the Virgin mountains, successively. The structure represented on these sections is the culmination of events which began far back in geologic time and throughout which a contrast has existed between the regions east and west of the backbone line. Before the Pennsylvanian, as Fig. 3 shows, there was a shallow shelf on the east and a deep marine trough on the west; after

Jan 1, 1935

By Augustus Locke, Paul Billingsley

The mining districts of the first order' of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of compressive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 Nature of the Thrust Arc The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The. cross-sections are as shown in Fig. 2. The backbone of the belt is the upward and eastward moving block represented by the Glacier Park, the Wasatch, and the Virgin mountains, successively. The structure represented on these sections is the culmination of events which began far back in geologic time and throughout which a contrast has existed between the regions east and west of the backbone line. Before the Pennsylvanian, as Fig. 3 shows, there was a shallow shelf on the east and a deep marine trough on the west; after

Jan 1, 1935

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,' and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.'.' Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett's No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

By P. G. Winchell, A. J. Heckler

An experimentally simple method for determining the effect of alloying elements on the activity of carbon is validated in Fe-Ni-C austenite. The technique consists of the equilibration of carbon between specimens of different nickel contents within a sealed silica capsule. The attainment of carbon equilibrium within each capsule is evidenced by: 1) in each capsule specimens of the same nickel content attained the same final carbon content regardless of their initial carbon contents, 2) in every capsule the final carbon content was reached for most nickel contents by carburizing and by decarburizing. The activity of carbon attained within each capsule was calculated from the carbon content of a binary Fe-C alloy placed within the capsule, and from the activity coefficient of carbon in the Fe-C system as found by Smith for CO/CO2/C equilibrium. The activity of carbon in Fe-Ni-C austenite determined by this method at 1000°C agrees with prior work by Smith, who used mother method. The measurements are extended to 800°and 1200°C. The activity coefficient of carbon 7c, in Fe-Ni-C austenite is given by: where xC is the ratio of carbon to metal atoms and XNi is the ratio of nickel to metal atoms and where the standard state is chosen such that yC = 1 as xc approaches zero in Fe-C alloys. This equation appears to be valid for xni < 0.3, and 1073° < T<1473°K. ThE activity of carbon in Fe-C austenite has been measured by smithL at 800°, 1000°, and 1200°C. Smith has also studied the effect of nickel on the activity A. J, HECKLER and P. G. WINCHELL are Graduate Student and Associate Professor of Metallurgical Engineering, respectively, School of Metallurgical Engineering, Purdue University, Lafayette, Ind. This paper is based on a thesis submitted ty,to Purdue University, in partial fulfillment of the requirements for the degree of M.S. in Metallurgical Engineering which A. J. HECKLER received from Purdue in January 1962. Manuscript submitted August 13, 1962. IMD of carbon in austenite at 1000°C. In both these studies the activity of carbon was fixed by a flowing CO-C02* *Gas mixtures of hydrogen and methane were also used in Ref. 1 but these results are not incorporated in Ref. 2 or in the present study. gas mixture. In the present work, Smith&apos;s results for Fe-Ni-C austenite are confirmed and extended to 800" and 1200°C by a different experimental technique. EXPERIMENTAL PROCEDURE In essence the experimental technique consisted of enclosing specimens of various nickel contents in an initially evacuated silica capsule and annealing the capsule until carbon equilibrium was attained among the enclosed specimens. The carbon activity obtained within the capsule was determined from the final carbon content of the binary Fe-C alloy included in each capsule and the results of smith.&apos; In order to evaluate this method the absence of nickel transfer between specimens must be established and the attainment of carbon equilibrium between samples must be assured. The absence of nickel transfer was demonstrated in the case of an originally pure iron sample which was annealed at 1200°C in a capsule with a 27.3 at. pct Ni alloy. The final nickel content of the iron specimen was less than 0.1 at. pct, a change which has a negligible effect on carbon activity. The attainment of carbon equilibrium was demonstrated within every capsule and in over half the results by achieving the same final carbon content in a sample which carburized during equilibration and in a sample of the same nickel content which decarburized during equilibration. The base Fe-Ni alloys were vacuum melted from Ferrovac E or electrolytic iron and Mond or electrolytic nickel. The samples were rolled and/or swaged and their carbon content adjusted to the desired pre-equilibration level either by methane-hydrogen carburization or by direct carbon transfer from a graphite source in a sealed silica capsule. As mentioned previously, high-carbon and low-carbon samples were prepared for most nickel levels in each capsule. The specimens were cleaned and

Jan 1, 1963

By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,&apos; kinetics,2&apos;3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6&apos;7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969

By T. P. Floridis, J. H. Young

The need for close control of the phosphorus content of steels has led to numerous investigations on the equilibria of the dephosphorization reactions. Winkler and chipman1 have established the general conditions for effective dephosphorization of steel. They are high slag basicity, high oxygen potential, and low temperature. Other investigators have made additional contributions to the understanding of the dephosphorization process. The current status of the understanding of the dephosphorization of steel is concisely presented by Bodsworth2 and by Ward. The investigation reported in this communication was undertaken with the purpose of establishing the effect of additions of barium oxide and calcium fluoride on the dephosphorizing capacity of slags. Esin and Gel&apos;d4 proposed that barium oxide, being more basic than calcium oxide, should cause an increase in dephosphorizing capacity when added to steelmaking slags, or when used as a substitute for calcium oxide. Derge5 has also proposed that in the future conventional slags might be replaced by BaO-Al2O3 slags. There is, however, no experimental evidence confirming the effect of barium oxide on the dephosphorizing capacity of slags. The effect of calcium fluoride on the dephosphorization of steel is not clearly understood. It is generally recognized that additions of calcium fluoride are beneficial. It is not clear, however, whether calcium fluoride affects the equilibrium of the dephosphorization reaction, or whether it simply causes an increase in the fluidity of the slag and, consequently, faster approach to equilibrium. The experimental procedure consisted in equilibrating synthetic molten slags with liquid copper at 1550°C under a gas stream containing argon, hydrogen, and water vapor. In all experiments the argon to hydrogen ratio was approximately 4:1, and the hydrogen to water ratio was 5.42:l. Molybdenum crucibles were used as containers for the slag and metal. Under the above-described conditions of temperature and composition of atmosphere, there was no observable attack of the crucibles by the metal, slag, or atmosphere. Copper was used instead of iron, because iron attacks molybdenum. The equilibration was made in a tubular furnace consisting of a recrystallized alumina tube. The alumina tube was heated by electrical resistance. A Pt-40 pct Rh wire winding was used for most runs. A silicon carbide tubular resistor was also used for some runs. Temperatures were measured with a Pt-Pt-Rh (10 pct Rh) thermocouple and kept constant within ±5°C. Equilibrium was approached from both sides, i.e., by adding the phosphorus either as oxide in the slag or as a phosphorus-rich alloy of phosphorus and copper. The holding time at the equilibrium temperature was 6 hr. At the end of each run the crucibles were rapidly cooled and removed from the furnace. The slag and metal were separated and analyzed. The experimental results are shown in Table I. The phosphorus content of the slag is expressed both as percent phosphorus pentoxide and as percent phosphorus. The basicity ratio is computed by dividing the number of moles of basic oxides-oxides of barium, calcium, magnesium, and sodium—by the number of moles of acidic oxides- oxides of aluminum, phosphorus, and silicon. Calcium fluoride is not included in the computation of the basicity ratio; i.e., calcium fluoride is assumed to be neither basic nor acidic. The distribution ratio of phosphorus—percentage of phosphorus in the slag divided by the percentage of phosphorus in the metal- is plotted in Fig. 1 against the basicity ratio. The results indicate that slags containing barium oxide have greater dephosphorizing capacity than slags containing calcium oxide. The high dephosphorizing capacity of slags containing sodium oxide and the low dephosphorizing capacity of magnesia-containing slags which already have been reported in the literature2 are confirmed by the results of this investigation. It appears that calcium fluoride has a beneficial effect on the distribution of phosphorus between slag and metal in acid slags only. Although the obtained distribution ratios between the phosphorus contents of slag and copper are not directly applicable to the dephosphorization of steel, they are sufficient for evaluating the effect of slag additions on the dephosphorizing capacity of slags in general. An increase in the ratio of distribution of phosphorus between slag and metal indicates lowering

Jan 1, 1968

By J. H. Bowden

The shaft-plant here described was put in operation in September, 1895, and the No. 6 slope-motor was started in May, 1896. The plant comprises : One Norwalk three-stage compressor l21/2, 91/2 and 5 in. diameters of air- and 20 in. diameter of steam-cylinder, all 24 in. stroke; capacity at 100 revolutions, 296 cu. ft. of free air per minute, compressed to 600 Ibs. per sq. in. A main pipe, 5 in. diameter, 4380 ft. long, with five charging-stations in No. 6 Shaft, and a branch of 3 in. pipe, 3100 ft. long, with three charging stations, in No. 6 Slope. These pipes on each line charge a Porter compressed-air motor, with 7 by 14 in. cylinders, and four 24 in. drivers, weighing about eight tons, with a tank-capacity of 130 cu. ft. of air at 550 lbs. pressure in the main tank, reduced to 160 lbs. in the 8-in. auxiliary tank of 4.2 cu. ft. capacity, supplying the cylinders. The No. 6 shaft run averages 4000 ft. each way on grades of $ to 23/4 per cent., and averaging close to one per cent. in favor of the loaded cars. The No. 6 slope run averages 2100 ft. with nearly the same grades. The mine-cars weigh 2800 Ibs. empty, and about 9800 lbs. loaded, and are hauled in trips of 12 to 20, averaging about 15 cars. The shaft-motor now hauls about 355, and the slope-motor 320 cars per day of 10 hours, replacing in the shaft 17 mules, and

Jan 1, 1901

By Gordon H. Chambers

MANGANESE ore is a true jack-of-all trades among industrial minerals, its only possible rival being iron ore. It is used in porcelain enamel, dry batteries, building brick, glazed pottery, floor tile, plastics, welding rods, chemicals, and varnish. You may be reading this through spectacles decolorized with manganese, and the light bulb above you contains some of this element. GEOLOGY Nearly all commercial manganese oxide deposits are of secondary origin; that is, they are concentrated by weathering from other manganese minerals more sparsely distributed in veins. The oxide minerals usually form irregular masses but in some places (Russia) they occur as beds of varying thickness and purity. Some manganese oxide bodies occur in soft gravel or clay formations but in other places the minerals are found in the form of veins and rounded nodules in limestone and other hard rocks. The geologic features of manganese deposits closely resemble those of iron deposits. Classification of the deposits is shown in the following table: I. Classification of manganese deposits based upon form of occurrence A. Stratiform masses 1. Oxides interlayered with sediments or layered volcanic or metamorphic rocks 2. Carbonates or silicates interlayered with sediments or layered volcanic or metamorphic rocks 3. Oxides, as surface bog deposits B. Veins and breccia filling 1. Oxides in larger part 2. Carbonates or silicates partly weathered to oxides C. Irregular masses 1. Oxides 2. Carbonates or silicates largely weathered to oxides D. Aggregates of small oxides in clay or weathered rocks 1. Mainly oxides E. Unclassified deposits II Classification of manganese deposits based upon mode of origin A. Hydrothermal deposits

Jan 1, 1949

JOINT convention week has become a feature of the year with western mining men. The first was held at Denver in 1926, the second at Salt Lake City in 1927, and the third is about to take place at Los Angeles. Holding in the same city in one week the meetings of a number of related organizations has been .found to permit the development of a well-rounded program at the same time that it economizes time and money for the members, many of whom belong to several of the participating organizations. For the third time, the American Mining Congress, represented by its Western Division, of which Philip Wiseman is chairman, is taking the lead and assuming the main responsibility. The A.I.M.E. is furnishing the papers for two sessions and the California Development Association for one. The Southern California Section, Robert R. Boyd, chairman, is host for the Institute, but the Northern California, Nevada and Arizona sections have each contributed papers to the program, and will be represented at the meeting. It will be a real reunion of the mining men of the Southwest.

Sep 1, 1928

By George C. Fryburg

The oxidation of platinum at high temperatures (above 800°C) is controlled by boundary-layer diffusion, except at the lowest pressures. The rate of oxidation is determined by the rate of diffusion of oxide through the boundary layer away from the platinum. This is in contrast to the situation in tungsten and molybdenum oxidation, where the rate is controlled largely by the diffusion of oxygen through the boundary layer towards the metal. The difference in mechanism is a consequence of the much lower rate of oxidation of platinum. Evidence is presented that supports this mechanism for the oxidation of platinum. SOME years ago we reported1 a study of the oxidation of platinum in ordinary oxygen in the temperature region above 800°C, where the oxide is volatile. All the data available up to that time had been obtained with platinum crucibles or plates heated in tube furnaces. The results were widely variant and highly dependent on the flow rate of gas through the furnace: the faster the gas flow rate, the higher the measured oxidation rate. These results indicated to us2 that reaction equilibrium was being approached in the furnace and that the rate was diffusion limited. To minimize these effects, we employed1 electrically heated ribbons placed in a cooled bulb. We were primarily interested in the low-pressure region, but some experiments were performed at pressures up to 1 atm. We found a peculiar pressure dependency which was explained on the basis that the rate of oxidation was proportional to the pressure at all pressures, but that with increasing pressure an increasing fraction of the volatilizing oxide was back-reflected to the ribbon by the surrounding gas molecules. The oxide molecules are not stable at the temperature of the platinum and are decomposed on impact, the platinum being re-deposited on the specimen. Because of the limitations of space, this explanation was offered summarily without detailed support. Recently, Jaffee and associates3, 4 have suggested that the pressure dependency of our data up to 0.5 torr could be explained on the basis of a Langmuir-type adsorption of molecular oxygen followed by dissociation. Since the correct explanation of the effect of pressure on the oxidation rate is a necessary requirement to the development of the basic mechanism of the oxidation reaction, we felt that the back-reflection theory should be presented in more detail. This is the object of the present paper. RESULTS AND DISCUSSION A typical set of results showing the pressure dependency of the oxidation reaction is presented in Fig. 1, where we have plotted, on logarithmic scales, the rate of oxidation, R, vs the pressure, p. For comparison some results of Krier and Jaffee4 and of Raub and plate5 are also shown. These data were taken at atmospheric pressure using furnaces. The effect of reaction equilibrium within the furnace is apparent from the much smaller values that these observers obtained: Raub and Plate In O2 found a rate of 3.1 µg cm-2 hr-1 compared to our value of

Jan 1, 1965

By B. M. Larsen, T. E. Brower

IN two previous papersl,2 dealing with the carbon-oxygen reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity 0[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm,; that is, if [C] X [O] is taken as 0.00222, 0[O] = [O] - 0,00222/[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.&apos; This quantity 0[O] proves to be substantially independent of carbon content over the range 0.08 to 1.2 per cent, as well as of the basicity of the slag, and is nearly always within the limits 0.015 to 0.025 per cent when the bath is boiling normally and is in what we have termed a steady state. Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, 0[O], on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in ?[O] level following addition of Spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. VARIABILITY OF EXCESS OXYGEN IN NORMAL OPEN-HEARTH OPERATION The preceding general statements refer to the average value of ?[O] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining oxygen from the gas phase above it, or from added ore, faster than it is losing oxygen to the metal; yet when the bath starts to boil vigorously, the opposite condition may prevail for some time. The consequence of this lag is a variation of ?[O], the interpretation of which in a single heat may not be immediately obvious, This condition is illustrated in Figs. I and 2. In Fig, I, ?[O] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small ore feed causes only a small rise in 0[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1946

By G. B. Walker

THE sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods.

Jan 1, 1949

By E. L. Mann

Asbestos is the generic name given to a group of fibrous mineral silicates found in nature. They are all incombustible and can be separated by mechanical means into fibers of various lengths and cross sections, but each differs in chemical composition from the others. The commercial grades of asbestos consist of a spectrum of lengths and sizes and are not definitive as are most organic fibers. It is generally recognized that there are two main groups of asbestos. The first only contains the fibrous serpentine called chrysotile and comprises about 94% of the world production of asbestos. The second group contains five minerals in the amphibole series-crocidolite, amosite, anthophyllite, tremolite, and actinolite. The latter two have no commercial importance. Properties Physical The structures of asbestos fibers have been studied intensively over a number of years. X-ray diffraction patterns have been used as a means of identification and classification. Low angle X-ray scattering techniques have shown that chrysotile fibers are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 18Å to 300 Å units, while the amphibole fibers are many times larger in cross section, have considerably smaller surface areas, and the fibers are less symmetrical than those of chrysotile. Electron micrographs of the more common types of asbestos are shown in Figs. 1-4. Fig. 1 illustrates the softness and flexibility of chrysotile which make it suitable for textile-type products. For a number of years there was considerable controversy over the exact nature of chrysotile fiber, but the photographic evidence in Figs. 5-7 clearly show that it is tubular in structure. The curvature is the result of the mismatch in the dimensions of the silica [Si2O5] and brucite [Mg(OH)2] layers which are on the inside and outside, respectively, of a double sheet. This curvature had been predicted by Pauling (1930) years ago based on the molecular dimensions of the two component structures. In contrast to this, the structure of the amphiboles consists of two ribbon chains based on Si4O11 units separated by a band of seven cations with two hydroxyl groups attached to

Jan 1, 1983