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ENGINEERS AVAILABLE (Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members.) Member, graduate engineer, aged 44, with over 22 years' experience in connection with the development of large coal and coke properties in different parts of the country, desires position as general manager or general superintendent of large bituminous coal producer, or will take an interest and the management of a smaller operation. No. 258 Member, aged 41, mining engineer, manager or general superintendent, 20 years' experience, 10 years in Mexico, 5 years Western States, 5 years abroad. Guarantee results, fluent Spanish, excellent references. New York interview. No. 282. Member, technical mining graduate, 10 years' experience, especially in design, erection, construction and purchase of power and mining equipment and supplies, desires position in purchasing department. Married, aged 32, employed at present, references furnished. No. 295.

Jan 6, 1916

By Ralph M. Barnett, Albert K. Smith

During the last few years, a great deal of interest has been aroused in the use of more refined blasting techniques. It has been the effort of many mining companies to reduce powder cost, obtain better rock breakage, reduce drilling costs and provide safer working places. With the advent of new types of powder and such techniques as cushion blasting, line blasting, smoothwall or soundwall blasting, and presplitting or preshearing, these goals are approaching reality. Smoothwall blasting and presplitting have re- ceived much attention at the Climax Molybdenum Co., Climax, Colo., mine because of the large cost factor involved. An experimental program was begun in 1961, and during 1964 to the present has been used in many working areas. Some spectacular results have been achieved by the operating personnel in hard ground, but the most beneficial results have been in areas where the ground has been soft and highly fractured.

Jan 7, 1965

By Robert W. Shearman

An historical record of the history of iron-and steelmaking in the United States has long seemed a desirable project to many in The metallurgical Society of AIME. Over a period of five years, experts in their fields have been asked to put down on paper their knowledge. The series of historical articles has been published in JOURNAL OF METALS, beginning with A. B. Wilder's article in 1956, marking the first one hundred years of Bessemer Steelmaking. The Electric Furnace Committee honored the first half-century of the use of the electric arc furnace in America during their 1956 Conference, and S. B. Casey, Jr., wrote an appropriate article for JOURNAL OF METALS. The historical series was well underway. Articles soon followed on the history of the blast furnace, on the open hearth furnace, and on ferro-alloy manufacture. The final need was an authoritative article on coke ovens. The publication of the five-part article by C. S. Finney and John Mitchell this summer has concluded our series (but not the march of progress). We now present, between two covers, a comprehensive historical review, the work of 13 authors. We are hopeful that this book will receive a welcome among ironmakers and steelmakers. and that it will be a valuable reference for home or office library. We hope also that students will find the material helpful in their studies of this most important of American industries. Perhaps also, the historian of Americana will learn something new in searching through these pages. We are indebted to our authors who have spent much time on historical research, and to their companies who have supported their endeavors. We acknowledge the support of the National Open Hearth Steel Committee and of the Blast Furnace. Coke Oven, and Raw Materials Committee in jointly assuming the financial risks in publishing this book.

Jan 1, 1961

By Herbert A. Everest

Discussion of the paper of HERBERT A. EVEREST presented at the New York meeting, February, 1916, and printed in Bulletin No. 109, January, 1916, pp. 165 to 167. NEWELL G. ALFORD, Earlington, Ky. (communication to the Sec-retary*).-Mr. Everest's statement concerning the economies in a small coal mine has interested me very much. The majority of discussions on coal-mine economy omit the small operator and for this reason Mr. Everest's paper should lead to productive thought. I agree that close concentration of working places and constructive supervision of labor are two items of salvation to the small operator. It is also true that small mines often yield as much profit per capital invested as their larger neighbors. Mr. Everest also says that the small operator has so keen a regard for the inroad on his profits that even one extra day hand is an extravagance not tolerated, and this is rightly so. But, does not this earmark of the small operator in many cases offer a clue to his vital weakness? A credit balance is the acid test of success in any enterprise. With the small operator who owns practically all the capital stock this is particularly significant. He never takes his eyes off the market price and at the same time strains every nerve to cut down his payroll. In several cases I have noted that the resultant close supervision of labor was in fact too close. The "stitch in time" was not applied to the repair of this or that, with a decided increase to the cost of the work when it had to be done at the expense of cutting off the run when orders were on the books.

Jan 5, 1916

By John T. Galey

In all, 210 wellst were completed in southwestern Pennsylvania during 1939, which is 59 more than were drilled during the preceding year. Of this number, 137 were gas wells, which is a considerable increase from the 81 completed during 1938. Only 25 oil wells were completed, as against 28 in the previous year, and 28 dry holes, 6 more than last year. Shallow Development—Gas The increase in the number of gas wells is largely the result of a search for additional gas in Armstrong and Indiana Counties. Although a considerable number of wells were drilled in the latter county, the majority of them produced less than 100 M cu. ft. initial open flow. In Armstrong County, a new pool was opened in Cowanshannock township, producing from the third Bradford sand. Several large wells were obtained there, one of which produced an initial of nearly 12 million cu. ft., with a reservoir pressure of 1100 Ib. However, the productive area has been fairly well outlined by further drilling and shows that the pool covers only about 800 acres. The sand is 20 to 30 ft. thick, and probably has 5 to 6 ft. of pay. Thus this reserve is not an important one. Several wells were found in Menallen township, Fayette County, where the Big Injun sand has been having a play for the past three years, but the activity there is much less than a year ago. Oil On the west side of the Bradford sand gas pool, Cowanshannock township, Armstrong County, a well was drilled which flowed 100 bbl. the first day from the Tiona sand. The probability is that this well is a freak, as the Tiona has been drilled within a fairly close distance on every

Jan 1, 1940

By John T. Galey

In all, 210 wellst were completed in southwestern Pennsylvania during 1939, which is 59 more than were drilled during the preceding year. Of this number, 137 were gas wells, which is a considerable increase from the 81 completed during 1938. Only 25 oil wells were completed, as against 28 in the previous year, and 28 dry holes, 6 more than last year. Shallow Development—Gas The increase in the number of gas wells is largely the result of a search for additional gas in Armstrong and Indiana Counties. Although a considerable number of wells were drilled in the latter county, the majority of them produced less than 100 M cu. ft. initial open flow. In Armstrong County, a new pool was opened in Cowanshannock township, producing from the third Bradford sand. Several large wells were obtained there, one of which produced an initial of nearly 12 million cu. ft., with a reservoir pressure of 1100 Ib. However, the productive area has been fairly well outlined by further drilling and shows that the pool covers only about 800 acres. The sand is 20 to 30 ft. thick, and probably has 5 to 6 ft. of pay. Thus this reserve is not an important one. Several wells were found in Menallen township, Fayette County, where the Big Injun sand has been having a play for the past three years, but the activity there is much less than a year ago. Oil On the west side of the Bradford sand gas pool, Cowanshannock township, Armstrong County, a well was drilled which flowed 100 bbl. the first day from the Tiona sand. The probability is that this well is a freak, as the Tiona has been drilled within a fairly close distance on every

Jan 1, 1940

By W. N. Logan

THE petroleum industry of Indiana made somewhat notable progress during the year 1923, considering the number of handicaps it encountered. The price of labor and materials continued to have an upward slant while the price of crude oil took a decidedly downward course. In spite of these adverse conditions, the quantity production will closely approximate that of 1922, when it passed the million-barrel mark. The progress of the industry in Indiana should be considered fairly satisfactory as long as the present production is maintained. In other words, if the loss of production from the waning old wells can be offset by the production from the new for a period of 10 or 15 years longer, the industry may have cause for congratulation. SUB-TRENTON INVESTIGATIONS In recent years a number of tests of strata lying below the Trenton limestone have been made in Indiana. Several of these tests were completed in 1923. Indications of oil were reported by drillers from several horizons below the Trenton. The most satisfactory of these came from the St. Peter sandstone lying immediately below the Trenton limestone, but no production has yet been obtained from any of the Sub-Trenton horizons. Glen Valley Wells.-Two wells in Marion County were drilled into the St. Peter sandstone, 1 mi. north of Glen Valley and 9 mi. south of Indianapolis. About 30 ft. of sand saturated with a dense asphaltic oil was found in the upper part of the St. Peter sandstone in one of the wells, which contained about 10 per cent. of the light oils, or more easily volatile constituents, and about 90 per cent. of a dark, dense, asphaltic residue. The oil resembled the residue of an asphaltic petroleum from which the more volatile oils had disappeared.

Jan 3, 1924

By K. L. Williamson, P. W. Dugan

INTRODUCTION In recent years there has been increased social awareness and government attention directed toward the mining industry. The growing influence of the Occupational Safety and Health Administration (OSHA), the Mine Safety and Health Administration (MSHA), and the Environmental Protection Agency (EPA) has resulted in volumes of regulations governing a multitude of health and safety aspects of mining and milling. These regulations naturally have had an impact on new plant design and in some cases have necessitated retrofitting of existing plants. This paper will not examine the regulations governing the industry, since they are a matter of public record, but rather will address two specific health considerations, dust and noise, and their influence on the design of crushing and screening plants. DUST AND NOISE CONCEPTS Dust is generally defined as finely divided solids which may become airborne without any physical or chemical change except fracture. Since the purpose of comminution circuits is to reduce the size of solids by fracture, a percentage of the material is normally reduced in size to a point where it can easily become airborne. The major cause of dust becoming airborne is the air induced by falling material. When granular material falls through a distance, the induced (or entrapped) air rushes out available openings, carrying with it the fine particles that have become suspended. For this reason, the major points of dust generation are the points where the material is falling: chutes, transfer points, screens and equipment feed and discharge points. The expected dust concentration in an area is a function of the degree of size reduction (i.e., finer particles are more readily carried by air currents than heavier particles) and the volume of air that is induced. The measured dust concentration values for various operations agree with this

Jan 1, 1982

By N. Plint, E. T. Pinkney

Copper segregation developments within the Anglo American Group are described with particular reference to the work of the TORCO Project Team. Some radical differences have been adopted in the mechan-ical approach as compared with methods used by previous workers. Most important among these are the following: (1) The heating unit is a fluidized-bed roaster. (2) A moving bed segregation chamber is used in which a packed bed of heated ore, to which reagents have been added, moves slowly downwards under gravity and is discharged at a controlled rate by means of a suitable valve mechanism. (3) The quantities of reagents used (sodium chloride and some form of carbon) are only a small fraction of those recommended by other investigators. (4) Retention times of only 2 min have been satisfactory for the complete segregation of many types of ore. Project TORCO is the code name given by Anglo American Corp. of South Africa, Ltd., to the investigation undertaken in Zambia to develop a plant capable of treating large tonnages of refractory copper-bearing ores by the segregation process. The process has now been under investigation for six years (1960-66) and during that period work has progressed from bench-scale laboratory tests through small-scale pilot-plant work to a 500-tpd commercial pilot unit. Test work has been carried out mainly on the ores of the Zambian Copperbelt and results have been encouraging. Recoveries on the order of 90% have been obtained on all Copperbelt ores tested with high concentrate grades. PRELIMINARY INVESTIGATION Laboratory scale segregation test work on Nchanga banded sandstone ore and oxidized ore from Kansan-shi was originally conducted by Professor Maurice Rey. SociCtC Miniere et Mktallurgique de Pefiarroya, in 1957. Both ores responded favorably to the process. In November, 1960, the consulting engineers of Anglo American Corp. of South Africa, Ltd., initiated preliminary investigations on the application of the segregation process to Copperbelt ores. In early laboratory work, samples were heated in a closed, externally heated tube furnace for one hour at temperatures ranging from 800 to 830°C. The free moisture content of the ore feed was 4% and reagent additions were 0.5% salt and 1.0% coal. Both salt and coal were pre-crushed to -48 mesh Tyler.* All samples except an ore from the Bancroft mine responded well to the process and recoveries of over 90% were obtained. The presence of dolomite was responsible for the relatively poor recoveries from the Bancroft ore, as tests on one of the other ores with additions of calcite or dolomite confirmed. Recoveries dropped from 94 to 45% Grades of all the rougher flotation concentrates produced were low at 10-15% copper. The laboratory investigation was then followed up on a pilot-plant scale. An attempt was made to carry out the segregation process in a coal-fired 5-ft-diam fluidized-bed roaster. The feed consisted of a banded sandstone from Nchanga to which 0.5% sodium chloride had been added. Reducing conditions were maintained in the roaster by the addition of coal in excess of that required for heating the feed. The excess coal and added salt constituted the segregation reagents and the temperature of the bed was held at approximately 750°C. Recoveries of copper and grades of concentrates were low. The reasons for lack of success were: (1) The reaction is a gaseous one and a fluidized-bed roaster is therefore unsuitable as a segregation unit. (2) Coal in excess of that required for heating was introduced into the fluidized bed and under these conditions some of the copper would be reduced in situ. The term "reduced in situ" is used here to describe any copper mineral reduced to the metallic state in its original site within the ore particles. If this copper is to be recovered by subsequent froth flotation it must first be liberated from the gangue by grinding or some other method which, in practice, is usually not feasible on ores of this type.

Jan 1, 1969

By A. R. Troiano, R. F. Hehemann

The influence of partial decomposition to high temperature bainite on reaction kinetics at a lower temperature has been studied in two alloy steels. Reaction at the lower temperature is retarded by the prior treatment, and the extent of decomposition may be reduced. Interpretation of these results is based on a mechanism involving a limitation in the nucleation and growth of bainite plates. OF the major transformations in steel, the characteristics and general behavior of the bainite reaction are probably the least understood and appreciated. Limitations of space preclude a critical evaluation of the present status of the bainite transformation in this presentation; however, such a treatment will shortly appear elsewhere. Only the salient features pertinent to the present investigation will be introduced briefly here. Although the reaction curve for the formation of bainite is similar to that for a nucleation and growth process, other kinetic features are more in keeping with the martensitic mode of transformation. A definite temperature exists above which austenite will not transform to bainite.1-5 his temperature, which has been designated B., is determined by the composition of the austenite. Unlike other nucleation and growth processes, the amount of austenite transformed to .bainite is a function of reaction temperature. The extent of decomposition increases from 0 at H. to 100 pct at some lower temperature.' , This lower temperature will be designated B1 and appears to be relatively insensitive to austenite composition.% 5 The similarity in the effect of reaction temperature on the bainite and martensite transformations serves to emphasize the close connection between these two decomposition processes. Austenite decomposition in the bainite range proceeds without partition of the alloying elements.8-11 Partition of carbon has been proposed" primarily on the basis that partial transformation to bainite lowers M, and increases the amount of austenite retained at room temperature. Carbon enrichment resuslting from such partition has been employed to explain the influence of reaction temperature on the extent of decomposition.'" It should be noted, however, that no enrichment has been detected experimentally in high carbon steels.1,14,15 Lattice-parameter measurements of retained austenite in steels containing 0.3 to 0.4 pct C have indicated carbon enrichment, 3,10-18 although the split indicative of a high carbon martensite has not been reported. Carbon enrichment, if it does occur, must be highly localized around the bainite plates. Therefore, carbon enrichment does not account for the influence of temperature on the progress of the bainite reaction."' Thermal history is known to influence the martensite transformation through stabilization.20,21 No similar phenomenon in the bainite transformation has been reported. Materials and Procedure Two triple-alloy steels were chosen for this investigation. Their compositions were as given in Table I. These steels were chosen because the pearlite reaction did not interfere with the bainite reaction. Steel K was received in the cast condition and forged from 2 in. square bars to 1/2 x1 3/4 in. plates. The 4340 was received as 11/4 in. hot-rolled rounds. Both steels were homogenized in vacuum for one week at 2300°F in order to minimize segregation. A quenching dilatometer similar to that described by Flinn, Cook, and Fellows" was employed for the kinetic measurements. Dimensional changes were detected by a differential transformer coupled with a high speed recorder. The dilatometer was mounted so that it could be transferred to any one of three furnaces: a nitrogen-atmosphere austenitiz-ing furnace and two salt-bath furnaces for isothermal transformation. Dilatometer specimens were 1/32 x 1/4x 1/2 in. with a gage length of 1.4 in. All specimens were nickel plated in order to minimize decarburization during austenitizing. The austenitiz-ing conditions consisted of 10 min at the temperatures given above. Austenitizing temperatures were controlled to 210°F and transformation temperatures to ±3ºF. The precision of the dimensional measurements was estimated to be ± 5 x105 in. per in. Results and Discussion Isothermal Transformation: The characteristics of the isothermal bainite reaction will be described

Jan 1, 1955

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,' and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By C. Graeme-Barber, R. L. Bell, T. G. Langdon

An analysis is made of the formulas and ,methods used to estimate the contribution of grain boundary sliding to the overall strain of a polycrystal. The errors involved in the approximations and/or ,mistakes in earlier work are assessed quantitatively so as to make possible the critical use of previously published data. SINCE it has been found that, under conditions of very slow creep, the strain due to grain boundary sliding (?gb) may contribute as much as 80 pct of the total creep strain,1,2 it is obviously important to have reliable methods for estimating this grain boundary strain. In two recent papers Stevens3,4 has drawn attention to the pitfalls encountered in assessing ?gb. He criticizes 1) the assumptions made in the derivation of some of the formulas for ?gb, and 2) the indiscriminate averaging procedures used for obtaining the quantities substituted in these formulas. These and further criticisms of earlier work are mostly valid. Unfortunately the only formulas and procedures recommended are either impossible or very difficult to apply in practice. Furthermore no attempt is made to assess the errors involved by the earlier approximations or mistakes, and so it is not possible to make critical use of any of these early dab. The present article attempts to improve on these shortcomings by reference to empirical verification of easily applied formulas whose theoretical derivations involve some otherwise unjustifiable assumptions, and by a quantitative assessment of the errors in previous work. DEFINITIONS First it is necessary to define the terms and symbols to be used. The choice of symbols preferred here is a logical combination and extension of the v introduced by McLean5 and the u by Brunner and rant.' In Fig. 1 the two grains X and Y are displaced by the sliding vector AC. u is the component of sliding resolved along the stress axis, v is that measured perpendicular both to the stress axis and to the specimen surface, and w is that measured perpendicular to the stress axis but in the plane of the surface. Two angles define the orientation of the grain boundary: 8, between the stress axis and the surface trace of the boundary, and +, the internal angle on a longitudinal section cut perpendicular to the surface. In computing the strain resulting from the boundary displacement at all the in- dividual boundaries in a polycrystal the components u, v, or w are sometimes averaged along a longitudinal line (i.e., parallel to the stress axis), sometimes along a transverse line, and sometimes at randomly chosen boundaries. Averages obtained in these three ways are given subscripts 1, t, and r, respectively. Stevens rightly calls attention to the possibility of non-equiaxed grain shapes either at the start or at the end of deformation. In this article all values of numbers of grains per unit length will refer to measurements made before deformation. The subscripts 1 and t will be used for the number of grains per unit length obtained along longitudinal and transverse lines, r for that obtained by averaging along a number of randomly directed lines. FORMULAS FOR ?gb ?gt, as a Function of u. An obvious truth is that cgb can, in principle, be obtained by summation of all the v components at the boundaries intersected by a longitudinal line of known length I, viz.: where nl is the number of grains per unit length, parallel to the stress axis, in the unstrained specimen. There are assumptions in the analytic derivation of Eq. [I] due to Brunner and rant' but ~achinger' arrived at Eq. [la] by a rigorous method. Unfortunately the experimental procedure required by Eq. [ la] proves very difficult as boundary migration tends to obscure the points at which the longitudinal line meets the grain boundary and the errors on such measurements tend to be large, see Fig. 2. For example, on a specimen of Magnox AL 80 at a creep strain of 9.7 pct, 300 measurements of u obtained from the points of intersection of a longitudinal line with the grain boundaries gave ul = 8.95 ± 3.58 pm, or an error of ±40 pct, at the 95 pct confidence limit. These large errors due to migration may be avoided by measuring u from the separation of the segments

Jan 1, 1968

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 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 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 C. E. Lawall

ONE of the most important developments in the coal industry during 1940 was the continued uptrend in the production of bituminous coal. Estimated production for the year is 450,000,000 tons, with an additional production of anthracite of 50,000,000 tons making a total of approximately 500,000,000 tons. This is an increase of 12.5 per cent over 1939. Despite an estimated decrease of about 3.5 per cent in anthracite production, all of the major coal-producing states had increases in production for 9140. The national defense program, with the consequent increase in industrial activity, undoubtedly had an important effect on the increased demand for coal.

Jan 1, 1941