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By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By R. E. Smallman, I. Milne

The deformation behavior of single crystals of Nb-Mo alloys has been investigated with particular reference to the influence of composition, orientation, and temperature. Strong solid-solution hardening was observed reaching a maximum at the equiatomic cotrlposition and can be attributed to the difference in atomic size between niobium and molybdenutrz. Changes in the form of stress-strain curve, as shown by a high work-hardening rate and restricted elongation to fracture, were observed at a composition of Nb-85 pct Mo and are attributed to the presence of MozC DreciDitate. Conjugate slip was only extensive in dilute alloy samples; at the 50/50 composition deformation rnainly occurred by primary slip, and the onset of conjugate slip gave rise to failure by cleavage on (100). The variation of yield stress of Nb-50 pet Mo with orientation was consistent with slip on (011)(111) slip systems. The temperature deperndence of the yield stress between -196" and 250°C was similar to that of pure bcc metals, but at a much higher stress level; no evidence for twinning %as found. IN recent years the deformation behavior of various pure metals in groups VA and VIA has received considerable attention, but surprisingly little work has been carried out on binary alloys made by mixing metals from the two groups. Such an investigation would be of interest since single crystals of metals of group VA have been shown to deform characteristically with a multistage deformation curve1"3 while a parabolic type of deformation curve has been reported for most of the group VIA metals.4'5 It has been suggested by Law ley and Gaigher~ that the difficulty encountered in obtaining multistage deformation curves for molybdenum in group VIA was possibly because of the presence of a microprecipitate of MozC which they observed even at carbon contents as low as 11 ppm. Recently a multistage deformation curve has been reported for molybdenum ," although the stages are not so definitive as those for group VA metals. The binary alloys of the particular refractory metals which have been investigated in single-crystal form include Ta-w,' Ta- Mo,' and Nb- Na." While a large amount of hardening was observed for alloys of the Ta-W and Ta-Mo systems, associated with room-temperature brittleness for alloys approaching the equiatomic composition, Ta-Nb remained ductile over the complete composition range with little or no solution hardening. Other systems have been investigated by hardness measurements on polycrystalline material and a discussion of the hardening of these alloys has been presented by ~udman." The purpose of the present investigation was to examine the deformation behavior of Nb-Mo alloys in detail, with particular reference to alloy composition and single-crystal orientation. In this way it was hoped to shed some light upon the restricted ductility of these alloy specimens. 1) EXPERIMENTAL PROCEDURE The starting materials were obtained in the form of beam-melted niobium rod and sintered molybdenum rod of suitable dimensions. Since niobium and molybdenum form a complete solid-solution series at all temperatures, alloy single crystals were produced by melting the two constituents together in an electron bombardment furnace (EBM). To produce specimens free from segregation a molten zone was passed over the length of each rod six times in alternate directions at a speed of 10 in. per hr. Typical specimens were analyzed for interstitial impurities by gas analysis and for metallic impurities by spectrographic analysis. The results of this analysis are shown in Table I. Many of the tensile specimens were also analyzed (after testing) by scanning the gage length in an electron beam microanalyzer, from which it was found possible to predict the approximate composition of a specimen from the original proportions of each element in the EBM. The tensile specimens were made with a gage length of 0.5 in. and diameter of 0.075 in., using a Servomet Spark machine. By careful machining on the finest range for the final i hr of this technique, surface cracks could be reduced to the level where they were easily removed by electropolishing in a solution of nitric and hydrofluoric acids. The specimens were strained at a rate of 10 4 sec-' using friction grips designed to prevent accidental straining and maintain a good alignment before straining. The orientations of the individual specimens tested are shown in Fig. 1 and the corresponding compositions listed in Table I1 together with collated experimental data. 2)RESULTS a) General Deformation Behavior. The effect of composition on the room-temperature deformation curves of similarly oriented specimens is shown in Fig. 2. The yield stresses of the pure constituents, while not the lowest reported to date, were at least comparable with existing data. Although the solution hardening was large for alloys at either end of the phase diagram, and comparable with the Ta-W solution-hardening data of Ferris et a1.,8 the low work-hardening rate characteristic of niobium was sustained until a composition of Nb-85 pct MO had been reached. Associated with the peak yield stress ob-

Jan 1, 1969

By Rudolph G. Wuerker

Charles T. Holland (Head, Dept. of Mining Engineeri*, Virginia Polytechnical Inst., Blacksburg, Va.) Mr. Wuerker has presented a very interesting discussion of the use of triaxial test methods for investigating the strength properties of rocks. Such methods, no doubt, eventually will develop considerable information of interest to those concerned with the design of mine layouts, particularly in the field of pillar design. From his discussion of my recent article, "Cause and Occurrence of Coal Mine Bumps" (Holland Mining Engineering 1958, p. 933-1002), it is evident that in one place at least I did not make my meaning clear to him and perhaps others. To clear the matter up I think it best to quote from the article, somewhat more fully than did Mr. Wuerker, as follows: "4) In actual operations — because rocksare not perfectly elastic, homogeneous, nor isotropic and because local yield does occur — the maximum stress as demonstrated by Phillips (Ref. 22, pp. 64, 65) and indicated by much experience in mining, does not occur at the walls of the opening but at a short distance inside the pillar. Furthermore, the maximum stress does not reach as great a value as theoretical considerations and laboratory experimental methods indicate.* Actual distance inside the pillar, measured from the wall, at which the maximum stress exists, has not been determined. Observations in many mines, however, indicate that this distance could have a mini-value of one to six or eight times the bed thickness and that it is probably affected by width and height of the opening, depth of cover, and relative values of the elasticity and plasticity of materials comprising the roof, floor, and coal seam. The actual value of the stress produced probably lies between the theoretical maximum and the average stress concentration that would be produced if the weight of the strata above the unsupported opening were evenly distributed over the pillars for a distance equal to the opening width." The footnote reference in the above quotation referred to the following: "*For example, the Pocahontas No. 4 coal bed in southern West Virginia is mined under cover up to 1800 ft thick. Development openings are driven 18 to 20 ft wide, and the bed is about 6 ft thick. According to the work of Panek, the tangential wall stress at mid-bed height under these conditions would reach values between 4000 and 5000 psi. Actual tests of 3-in. cubes of this coal show its compressive strength would be much less than this, perhaps as low as 400 psi. Yet the pillars usually show no evidence of failure in these headings. In this same bed at a depth of 800 ft, the author has seen an opening 225 ft between supports lying between two old groves approximately 1100 ft apart. According to the theoretical considerations, the stress in the pillar walls would have been about 18,000 psi, yet the pillar showed little or no evidence of weight. In view of these observations, it is clear that the wall stress does not attain the maximum values indicated by theory." (Underlining added to original wording.) By referring to Fig. 2A of my paper it will be noted that theoretically the maximum pillar stress would occur at the pillar wall, i.e., at the passageway surface of the pillar. Obviously this cannot be correct in the cases of stress ranging from 4000 to 18000 psi since the coal at the surface of the pillar is under no constraint and cannot have a strength much greater than 400 or 500 psi. Hence, my conclusion that the maximum stress does not occur at the wall but back in the pillar some distance from the wall. Since these stresses are pushed back in the pillar from the wall, it is also obvious that the loads transferred to the pillar from the opening will be spread over a greater area and hence Pillar stresses will not rise to the values postulated by theory and photoelastic experiment. Further since to visual inspection the coal along the pillar wall did not appear to be failed the conclusion was reached that the stress shift was caused by local elastic or plastic yield and by difference in the elastic modulus of the rocks composing the mine floor, mine roof, and coal bed. Later on under the heading "Strength of Mine Pillars" (pages 1000-1002) the effects of constraint is briefly described. Also a formula taking into account constraint is developed relating pillar strength to the uniaxial strength of coal and the L/T ratio of the pillar. Since my paper was written, reports of experiments conducted in South Africa (Denkhaus, et. al., 1959), in Sweden (Hast 19581, and in Canada (McInnes, et.al., 1959) reveal that the conclusion expressed relative to the existence of a low stress area existing around the edges of pillars and solid faces as described above is generally correct. But it seems possible that where the wall stress developed is less than the unconfined strength of the rock composing the pillar and where the roof, floor, and pillar

Jan 1, 1961

By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964

By George Simkovich

It was hypothesized that solid-state point defects should alter the flotation properties of solids. Tests conducted on pure AgCl and AgCl doped with CdC12 show that atomic point defects exhibit an important role in the floatability of AgC1. Tests conducted on PbS doped with Ag2s or Bi2S3, also show that the defect structures resulting from these dope additions, i.e., a combination of electronic and atomic point defects, contribute significantly to the flotation of PbS. IT has been established that flotation occurs only when a finite contact angle exists between a solid and a gaseous bubble.&apos; This angle, measured through the liquid phase, is expressed by the equation where the are inter facial free energies and the subscripts S, G, and L represent solid, gas, and liquid phases, respectively. As is seen in Eq. [I] three interface free energies, sG, sl, and GL, enter into the contact angle equation. Therefore, any variation in these energies which sufficiently varies the contact angle will, in turn, vary flotation processes. Changes made in any of the phases concerned, i.e., gas, liquid, or solid phase, are reflected through the changes occurring in two of the surface energy terms. Thus, a change in the liquid composition would be noted in sL and GL, and it is this phase, the liquid, which is most frequently altered in flotation studies., Changes in the solid phase must be reflected through the changes occurring in the sG and sL terms. In particular, it is hypothesized that changes in the surface concentrations of point defects in the solid-phase will alter the sG and sL terms which, in turn, will be reflected by flotation results. As an illustration of this hypothesis one may consider the defect structure and the flotation of AgC1. The bulk defect structure of AgCl is essentially one involving equal number of cation vacancies and interstitial cations.3 Upon adding CdC1, to AgC1, a greater number of silver ion vacancies are created in the bulk of the crystal.4 On the surface of the crystal the smaller binding forces and the free space accomodations may also allow for the creation of "surface interstitial anions", which will be designated as ad-anions. Thus, the point defect structure of the surface of AgCl doped with CdCl, will consist of cation vacancies and/or adanions. If the molecular forces responsible for the surface energies, ?SG and ?sL, are significantly altered by the presence of these surface point defects, then differences in flotation results will be noted as the concentration of these defects is varied. The defects present in AgCl are predominantly atomic in nature. In the case of PbS both electronic and atomic defects are present.5 This compound conducts electrically by either electrons or electron holes depending upon whether excess lead or excess sulfur is present. Upon disolving BiS3 in stoichio-metric PbS, one increases the concentration of cation vacancies and the number of electron carriers in the bulk of the crystal.5" At the surface, the possibility of ad-anions must also be considered. Conversely, upon dissolving AgS in stoichiometric PbS one increases the concentration of interstitial cations and the number of electronhole carriers in the bulk of the crystal.5,6&apos; At the surface the interstitial cations will be designated as ad-cations. Thus, the point defect structure of the surface of a PbS crystal doped with Bi2S3 will consist of a number of cation vacancies and/or ad-anions and an excess of electrons. Conversely the point defects on the surface of a PbS crystal doped with Ag2S will consist of a number of ad-cations and an excess of electron holes. Again, as in the case of AgC1, should the molecular forces responsible for the magnitude of the interface free energies, ?sG and ?sL, be significantly altered by the presence of these surface defects then significant differences in flotation results will be noted as the concentration of these defects is varied. EXPERIMENTAL To test this hypothesis flotation tests were conducted on pure and doped AgCl and on PbS doped with either Bi2S3 or Ag2S. Preparation of the AgCl samples was performed as follows: AgCl and weighed amounts of CdC1, were melted in a porcelain crucible. The melt was then forced through a capillary tube and the particles emitted solidified in air as they fell about 1.5 meters. Spherical particles, -0.50 + 0.25 mm, were separated from the remaining solidified material

Jan 1, 1963

By J. G. Eenink, R. A. Cunningham

One phase has been completed of a laboratory invesrigation of formations with relatively high permeability under conditions of overburden, formation and mud coltrmn pressures. The following statements are based on these tests within the limitations described. Drilling rate decreased when mud column pressure was greater than formation pressure. The decrease was primarily due to a layer of cuttings and mud particles held to the hole bottom by the difference in pressure. Much of the force of the bit was wasted in this layer and was unavailable for penetrating virgin formation. Adequate jet velocities helped clean the filter cake and chips away and resulted in increased drilling rate — the higher the jet velocity the faster the drilling rate. Drilling rate increased slightly when formation pres sure was greater than mud column pressure. The i11(reuse resulted from cleaning the hole bottom as formarion fluid flowed into the borehole. Overburden pressure had practically no effect on drilling rate. INTRODUCTION Some formations are difficult to drill in a wellbore hole but are easily drilled under atmospheric conditions in the laboratory. The reasons for this apparent difference in drillability are not fully understood. An increase in formation compressive strength causes a reduction in drilling rate. It has been shown by Griggs1, Handin2 and others3-1 that formation strength increases under conditions of high hydrostatic stress. Based on these results, a decrease in drilling rate would be expected with increased drilling fluid pressure in formations of low permeability having low formation fluid pressure. Such a decrease has been shown by Murray. et a1 and Eckel" This effect holds even when using nitrogcn under high pressure as the drilling fluid (unrc-ported tests from the Hughes laboratory). Poor bottom-hole cleaning may account for decreased drilling rates. Even though it may not be easily explained, evidence of poor cleaning can easily bc seen. One evidence is the increased drilling rate that accompanies decreased balling obtained with addition of oil in some muds used to drill shales.4,7,3 Many variables can affect drilling rates. These may include mud composition and properties, formation properties, bit types and operating conditions, formation fluid, mud column and overburden pressures. These must be studied a few at a time under carefully controlled conditions which simulate actual conditions as closely as possible. The purpose of this work was to investigate effect of overburden, formation and mud column pressures on drilling rates in permeable formations. These tests were suggested by conditions shown in Fig. I. Represented is a borehole drilled into a formation with relatively high permeability. In the vicinity of the hole bottom there exists a mud column pressure, P a formation fluid pressure, P and an overburden pressure, The mud has low water-loss properties and sufficient weight to more than overbalance the formation pressure. Laboratory investigation included a range with formation pressure greater than mud column pressure. NOMENCLATURE Pm mud column pressure = pressure of drilling fluid or mud at hole bottom Pf, formation pressure = pressure of fluid in intersticies of formation

By Alfred H. Bell, Virginia Kline

In 1944, Illinois produced 77,413,000 bbl. of oil, or 4.6 per cent of the total for the United States, and continued to rank sixth in the nation in oil production. This represents a decrease of 6 per cent from 1943, when- the total Illinois production was 82,256,000 bbl. This decrease was much less than the 23 per cent decrease in 1943 from production of the previous year. The principal factor in arresting the production declinc, which had been going on since 1941, seems to be the increased drilling that followed the relaxing of the Federal Government&apos;s rules in regard to well spacing. The daily average production for 1944 was approximately 212,000 bbl. Daily averages by months were as follows: Jan......... 219,000 July........ 206,000 Feb......... 220,000 Aug......... 211,000 Mar........ 216,000 Sept......... 209,000 Apr......... 211,000 Oct......... 210,000 May........ 213,000 Nov........ 209,000 June........ 209,000 Dec......... 205,000 During the year, 1991 wells were drilled for oil and gas in Illinois as compared with 1791 in 1943, an increase of II per cent. Of the 1991 wells, 430 are classified as "wildcat" as compared with 461 in 1943. Twenty-eight new pools (Table 2 A) were discovered in 1944 as compared with 29 in 1943. Changes in federal drilling regulations, permitting closer spacing of wells, resulted in a drilling program that emphasized development of proved acreage rather than wildcatting. Data on production and drilling by fields are given in Table I; data on annual production and drilling for Illinois, in Table 3. Discoveries Twenty-eight new fields (Table 2 A), 42 extensions (Table 2 B), and 39 additional producing zones in existing fields (Table 2 C) were discovered in 16 counties in Illinois during 1944. Of the 28 new fields, one was abandoned during the year, 14 were one-well fields, eight others had not more than 6 wells, one had 8, one had 9, one had 11, one had 15, and the largest new field, Roaches North, had 28 producing wells at the end of the year. In all, 109 wells were producing in these new fields on Jan. 2, 1945, as compared with 111 wells producing from 29 new fields at the end of 1943. . The average initial production of the discovery wells of the 28 new fields was 129 bbl. of oil and II bbl. of water, a notable decline from the average initial production of 194 bbl, of oil and 15 bbl. of salt water for the 1943 discovery wells. In fields discovered since 1936, the total number of oil wells producing at the end of 1944 was 12,335. Productive Acreage The area of proved production in the new fields (discovered since 1936) increased from 144,335 acres at the end of 1943 to 173,485 acres at the end of 1944 (Table I), an increase of 29,150 acres. Of this increased area, 1720 acres are in fields discovered during 1944 and 27,430 acres are in extensions of fields discovered earlier.

Jan 1, 1945

By I. Nilsson, G. Sundkvist, A. Danielsson

A spectrochemical method of slag analysis is descibed which utilizes fusion of the sample with a flux, then cooling and crushing to put all samples into a common form. The powder, is then fed onto adhesive tape and passed through a spark by means of a special device to provide very reproducible discharge conditions. Combined with a direct-reading optical emission instrument, this system provides speed and accuracy of antilysis heretofore unobtainable for. slag samples by any other method. THERE are many suggested methods for spectro-chemical analysis of slags. The most important are fusion-pellet methods and solution methods. In our company the fusion-pellet method has been used earlier, and is described by Lounamaa. W. H. Tingle and C. K. Matocha have made refinements of the pellet method.&apos; A Committee of the British Iron and Steel Research Association has investigated different methods of spectrochemical analysis of slags. Its purpose was to formulate a method which would give the complete analysis in 30 min with an accuracy of ±3 pct. The committee recommends a solution technique, which was thought to correspond best to their requirements. The method to be described is a fusion-tape method. The sample is isoformed by fusion and grinding. The powder is analyzed with the tape technique. The tape machine and some of its applications are described earlier.4&apos;5 The powder to be analyzed is continuously fed onto a moving adhesive tape, which passes through the spark gap. The sparks break through the tape and vaporize and excite the material to be analyzed. The most outstanding feature of the tape machine is its very high reproducibility. The concept of isoformation has been introduced earlier.= It means a pretreatment of the samples to make them uniform from the spectralanalytical point of view, i.e., cancelling systematic differences between the samples. The purpose of the isoformation is to reduce the influence of particle size, as well as chemical and mineral composition. Before describing the isoformation by fusion plus grinding, which is the purpose of this paper, a few words will be said about two other types of isoformations, i.e., grinding with buffer and ion exchange plus grinding as they have been considered during the application of the tape technique for slag analysis. Grinding with buffer might be a sufficient isoformation in some special cases, where the mineral composition is defined. The time of grinding must, however, be rather long, at least 5 to 10 min, even when using such an efficient mill as the Swing Mill from Messrs. Siebtechnik, Mühlheim, Germany. This type of isoformation is not recommended due to its limitations and due to the fact that the gain in time compared with the fusion technique is almost negligible. The principle of ion exchange plus grinding and some of its applications have been described.5 The following elements of interest in slag analysis can be determined in this way: Na, K, Cu, Mg, Ca, Ba, Zn, Pb, Al, Cr, Mn, Fe, Co, Ni. The very important element Si, however, cannot be analyzed with this method. Although the ion exchange isoformation for slag analysis cannot be looked upon as a routine method, it can be used for

Jan 1, 1962

By R. S. Hooper

IN attempting to describe recent mining developments at the Bunker Hill mine, it may be well to recall first the old days of hand mining when holes were laboriously drilled by hand to a maximum depth of three feet, and were shot one or two at a time, in order that the miner could take advantage of every slip, crack or bedding plane, and so save as much drilling as possible. Broken muck, of course, was loaded by hand shoveling into wheelbarrows or small cars, and heading advances or stope ton¬nages were governed by the number of men that could find room to work in any given place. The first big improvement over these old methods was the introduction of the reciprocating type of air-powered rock drill. This innovation, crude as it was, enabled the miners to set up a machine and drill a complete round of holes in one shift; but broken muck was still loaded by hand, and the size and rate of advance in headings were limited by time required to remove the broken rock. The next improvement of consequence was the appearance of the hammer-type rock drill, which greatly increased drilling speed over the reciprocating type, and made possible the completion of a full cycle in one shift, by the use of crossbars in headings, and permitted drilling and mucking to be carried on at the same time. Rock drills continued to improve as time passed, and finally the smaller and more efficient mucking machines appeared on the scene, and it became possible to muck out a round of broken rock and have a clean setup for one or more drill columns and machines. A complete cycle of mucking, drilling, and blasting was completed in one shift with an average advance of five feet. These conditions prevailed for several years, but as the mine grew deeper, the distances to transport the workers grew longer, and this fact together with the shortening of the working day, soon presented the problem of attempting to complete a cycle of operations in a shift of only six hours at the working faces. Anticipating this condition, the operating heads at the Bunker Hill had started an intensive study of more and better mechanization, and over a period of comparatively few years have adopted and placed in service methods and machines that make it possible for a three-man crew to consistently advance headings seven by nine feet in cross section, at the rate of eight feet, and more, per shift, doing all the mucking, switching, drilling and loading. These improvements consist of the following major items: I. The development of a light, flexible, easily transported jumbo equipped with pneumatic columns (Fig I), that has decreased the "setting up" and "tearing down" time an average of 1 1/2 hr per shift, or 25 pct of the available working time. These jumbos were developed at the Bunker Hill mine by members of the staff and consist of two pneumatic columns attached to a suitable carriage. They fold

Jan 1, 1947

By R. S. Hooper

In attempting to describe recent mining developments at the Bunker Hill mine, it may be well to recall first the old days of hand mining when holes were laboriously drilled by hand to a maximum depth of three feet, and were shot one or two at a time, in order that the miner could take advantage of every slip, crack or bedding plane, and so save as much drilling as possible. Broken muck, of course, was loaded by hand shoveling into wheelbarrows or small cars, and heading advances or stope tonnages were governed by the number of men that could find room to work in any given place. The first big improvement over these old methods was the introduction of the reciprocating type of air-powered rock drill. This innovation, crude as it was, enabled the miners to set up a machine and drill a complete round of holes in one shift; but broken muck was still loaded by hand, and the size and rate of advance in headings were limited by time required to remove the broken rock. The next improvement of consequence was the appearance of the hammer-type rock drill, which greatly increased drilling speed over the reciprocating type, and made possible the completion of a full cycle in one shift, by the use of crossbars in headings, and permitted drilling and mucking to be carried on at the same time. Rock drills continued to improve as time passed, and finally the smaller and more efficient mucking machines appeared on the scene, and it became possible to muck out a round of broken rock and have a clean setup for one or more drill columns and machines. A complete cycle of mucking, drilling, and blasting was completed in one shift with an average advance of five feet. These conditions prevailed for several years, but as the mine grew deeper, the distances to transport the workers grew longer, and this fact together with the shortening of the working day, soon presented the problem of attempting to complete a cycle of operations in a shift of only six hours at the working faces. Anticipating this condition, the operating heads at the Bunker Hill had started an intensive study of more and better mechanization, and over a period of comparatively few years have adopted and placed in service methods and machines that make it possible for a three-man crew to consistently advance headings seven by nine feet in cross section, at the rate of eight feet, and more, per shift, doing all the mucking, switching, drilling and loading. These improvements consist of the following major items: I. The development of a light, flexible, easily transported jumbo equipped with pneumatic columns (Fig I), that has decreased the "setting up" and "tearing down" time an average of 11/2 hr per shift, Or 25 PCt of the available working time. These jumbos were developed at the Bunker Hill mine by members of the staff and consist of two pneumatic columns attached to a suitable carriage. They fold

Jan 1, 1949

By H. G. Landua, Leah L. Naugle, H. H. Lowry

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its (&apos;Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By Leah L. Naugle, H. H. Lowry, H. G. Landua

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its (&apos;Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By S. S. Clarke

Late in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of Jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of Jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1949

By J. L. Foster, G. R. Gray, T. S. Chapman

The wall-building properties of salt-water drilling muds can be improved markedly by the addition of: (I) natural gums, such as traga-canth, karaya, and ghatti; (2) seaweeds, such as Irish moss; or (3) gelatinized starch. Results of laboratory tests have been confirmed by field trials. For drilling operations in which the mud becomes contaminated by salt, either through penetrating salt-bearing rocks or by addition of sea water to the mud, the added cost resulting from the use of one of the substances listed above is more than offset by freedom from stuck drill pipe and ease in running casing. Introduction It has been recognized for many years that oil production might be seriously hampered by infiltration of water from the drilling mud.l-4 As knowledge of the mechanism of the wall-building process advanced, methods were developed for evaluating the filtration characteristics of muds.5-ll The wall-building properties of freshwater muds are commonly regulated by the addition of bentonitic clays, or of agents to promote the dispersion of the natural mud solids. When strata bearing soluble salts are encountered in the course of drilling, the salts are incorporated in the mud; the clay solids are flocculated and water loss is increased tremendously. Methods gen-crally used in controlling filtration of freshwater muds are no longer applicable. The problem of reducing water loss from salt-water muds is not confined to any particular area, but is acute in parts of West Texas. Salt beds several hundred feet thick must be penetrated before the oil-bearing formation is reached. Since the formation drilled does not provide mud-making material, it is necessary to use large quantities of commercial clays, and even the best commercial clay does not afford relief from the problem of high filtration. A laboratory study has been made of methods of improving the filtration characteristics of salt-water muds, and some of the methods have been used in field practice. Laboratory Investigations Procedure Inasmuch as the immediate object of the investigation was the development of means of improving the wall-building properties of muds used in West Texas, an attempt was made to employ muds in the laboratory study comparable to those in field use. Samples of muds used in drilling the producing formations in six wells were secured. The properties of these samples are summarized in Table I, which lists the densities, viscosities, filtrations, and analyses of the filtrates for calcium, chloride, and sulphate. Viscosity was measured in the Stormer viscosimeter at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester8 at a pressure of 100 lb. per sq. in. Filtration rates are considerably higher than those of usual fresh-water muds, which amount to about 20 C.C. in 30 min. Water loss was so rapid in samples 4, 5 and 6 that filtration was complete in less than 10 min. and the values for 30 min. were extrapolated from the rates at shorter

Jan 1, 1942

By G. R. Gray, T. S. Chapman, J. L. Foster

The wall-building properties of salt-water drilling muds can be improved markedly by the addition of: (I) natural gums, such as traga-canth, karaya, and ghatti; (2) seaweeds, such as Irish moss; or (3) gelatinized starch. Results of laboratory tests have been confirmed by field trials. For drilling operations in which the mud becomes contaminated by salt, either through penetrating salt-bearing rocks or by addition of sea water to the mud, the added cost resulting from the use of one of the substances listed above is more than offset by freedom from stuck drill pipe and ease in running casing. Introduction It has been recognized for many years that oil production might be seriously hampered by infiltration of water from the drilling mud.l-4 As knowledge of the mechanism of the wall-building process advanced, methods were developed for evaluating the filtration characteristics of muds.5-ll The wall-building properties of freshwater muds are commonly regulated by the addition of bentonitic clays, or of agents to promote the dispersion of the natural mud solids. When strata bearing soluble salts are encountered in the course of drilling, the salts are incorporated in the mud; the clay solids are flocculated and water loss is increased tremendously. Methods gen-crally used in controlling filtration of freshwater muds are no longer applicable. The problem of reducing water loss from salt-water muds is not confined to any particular area, but is acute in parts of West Texas. Salt beds several hundred feet thick must be penetrated before the oil-bearing formation is reached. Since the formation drilled does not provide mud-making material, it is necessary to use large quantities of commercial clays, and even the best commercial clay does not afford relief from the problem of high filtration. A laboratory study has been made of methods of improving the filtration characteristics of salt-water muds, and some of the methods have been used in field practice. Laboratory Investigations Procedure Inasmuch as the immediate object of the investigation was the development of means of improving the wall-building properties of muds used in West Texas, an attempt was made to employ muds in the laboratory study comparable to those in field use. Samples of muds used in drilling the producing formations in six wells were secured. The properties of these samples are summarized in Table I, which lists the densities, viscosities, filtrations, and analyses of the filtrates for calcium, chloride, and sulphate. Viscosity was measured in the Stormer viscosimeter at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester8 at a pressure of 100 lb. per sq. in. Filtration rates are considerably higher than those of usual fresh-water muds, which amount to about 20 C.C. in 30 min. Water loss was so rapid in samples 4, 5 and 6 that filtration was complete in less than 10 min. and the values for 30 min. were extrapolated from the rates at shorter

Jan 1, 1942

By Lawrence B. Wright

The Republic district, Washington, is of new interest because of the discovery of new gold-silver ore within a unique structural pattern. The camp was revived in 1937 fol1owing installation of a plant to treat low-grade disseminated ore at Knob Hill and further stimulation followed discovery of "cross vein" breccia ores in 1939. Previous writers 1-2 ascribed the quartz veins to a latite porphyry stock, but are in disagreement as to its precise location and extent. This study leads to the conclusion that the ores have a more profound parentage linked to a broad system of thrust faults and folds, the mechanical origin of which is related to a southward trending (Sanpoil) syncline connecting with the Lewis and Clark zone of shift described by Billingsley and Locke3 in 1939. The Republic anticliue and a cross anticline recumbent against Cretaceous granodiorite. and involving some 4000 ft of Eocene andesite flows and early Miocene lake beds, localize the ores, mainly along the east flank, in a series of openings simulating drag folds and steeper than the folded flows. These broad structural features no doubt reach deeply into the basement rocks, where at appropriate crossings and junctions it is suggested that heat effects gave rise to ore-making materials, including, in this instance, intrusive breccias that later were mineralized, and comprising the broader bodies of new ores. The breccia ore is seen crosscutting the earlier narrow quartz veins with a welding of the two at junction areas by a second surge of ore minerals. The ore mined and developed since 1937 equals district production from 1896 to 1937 The ores are typified by cherty quartz, adularia and some barite, with fine pyrite and marcasite, polybasite, pyrargyrite, tetrahedrite and gold. Selenium is present, possibly with gold, as a normal selenide. The disseminated ores, as well as the vein and breccia ores, are localized principally in one 500-ft flow (Knob Hill andesite), which has been traced around the crest of the low northward-plunging Republic anticline. The gold-silver ratio in the earlier narrow veins is about I to 4 and in the disseminated and breccia ores, I to 7. The latter higher silver ratio is deemed to reflect the character of the second surge of mineralization. Sills and dikes of the Columbia River (Miocene) basalt cut the folded structure and ore, thus placing the mineralization in the middle Miocene. Introduction The Republic district of north central Washington is of new interest because of the discovery, development and extraction of new gold-silver ore; also, because of a unique local structural pattern believed to be integral with the broader tectonic mechanism of the continental framework. This district had 40 years of modest rating following its discovery in 1896. Its narrow ore bodies, complex mineralogy. and early inadequate metallurgy, together with the apparent bottoming of ore near 1000 ft, limited production to 300,000 oz of gold and 1,000,000 oz silver between 1897 and 1914. The camp was then reduced to lease Life until 1937, when the gold price increase of 1933 to $35 per ounce

Jan 1, 1949

By Lawrence B. Wright

The Republic district, Washington, is of new interest because of the discovery of new gold-silver ore within a unique structural pattern. The camp was revived in 1937 fol1owing installation of a plant to treat low-grade disseminated ore at Knob Hill and further stimulation followed discovery of "cross vein" breccia ores in 1939. Previous writers 1-2 ascribed the quartz veins to a latite porphyry stock, but are in disagreement as to its precise location and extent. This study leads to the conclusion that the ores have a more profound parentage linked to a broad system of thrust faults and folds, the mechanical origin of which is related to a southward trending (Sanpoil) syncline connecting with the Lewis and Clark zone of shift described by Billingsley and Locke3 in 1939. The Republic anticliue and a cross anticline recumbent against Cretaceous granodiorite. and involving some 4000 ft of Eocene andesite flows and early Miocene lake beds, localize the ores, mainly along the east flank, in a series of openings simulating drag folds and steeper than the folded flows. These broad structural features no doubt reach deeply into the basement rocks, where at appropriate crossings and junctions it is suggested that heat effects gave rise to ore-making materials, including, in this instance, intrusive breccias that later were mineralized, and comprising the broader bodies of new ores. The breccia ore is seen crosscutting the earlier narrow quartz veins with a welding of the two at junction areas by a second surge of ore minerals. The ore mined and developed since 1937 equals district production from 1896 to 1937 The ores are typified by cherty quartz, adularia and some barite, with fine pyrite and marcasite, polybasite, pyrargyrite, tetrahedrite and gold. Selenium is present, possibly with gold, as a normal selenide. The disseminated ores, as well as the vein and breccia ores, are localized principally in one 500-ft flow (Knob Hill andesite), which has been traced around the crest of the low northward-plunging Republic anticline. The gold-silver ratio in the earlier narrow veins is about I to 4 and in the disseminated and breccia ores, I to 7. The latter higher silver ratio is deemed to reflect the character of the second surge of mineralization. Sills and dikes of the Columbia River (Miocene) basalt cut the folded structure and ore, thus placing the mineralization in the middle Miocene. Introduction The Republic district of north central Washington is of new interest because of the discovery, development and extraction of new gold-silver ore; also, because of a unique local structural pattern believed to be integral with the broader tectonic mechanism of the continental framework. This district had 40 years of modest rating following its discovery in 1896. Its narrow ore bodies, complex mineralogy. and early inadequate metallurgy, together with the apparent bottoming of ore near 1000 ft, limited production to 300,000 oz of gold and 1,000,000 oz silver between 1897 and 1914. The camp was then reduced to lease Life until 1937, when the gold price increase of 1933 to $35 per ounce

Jan 1, 1949

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The times at which the first detectable amount of a phase forms at temperatures between 900° and 1800°F were determined. Both X-ray diffraction and metallography were used to detect a in highly strained filings; metallography alone to detect it in annealed bulk samples of six different types of stainless steels. The a phase was found to form in accordance with the C-type reaction curve in both austenitic and ferritic alloys. In filings of types 304, 347, and 446, a formed in a few hours, and in types 316, 309, and 310, it formed in a matter of minutes at temperatures corresponding to the knee of the C-curve. Only in the bulk type 309 steel, after 500 hr, and in the bulk type 310 steel, after as short a time as 25 hr at temperature, was n detected; in both instances at approximately the same optimum temperature as in the filings. The annealing temperature affected a phase nucleation only for the filings of type 304 and 347 steels, and for the bulk samples of type 309 and 310 steels. KNOWLEDGE of both the rate of nucleation and the rate of growth of the new phase is required for a complete description of metallurgical rate phenomena. However, data on the time for nucleation alone may frequently be useful in evaluating the tendency of commercial stainlcss steels to form s under various conditions. Very little correlated information of this type is available in the literature. Shortsleeve and Nicholson&apos; indicate that s forms in ferritic 24, 27 and 30 pet Cr steels according to a C-type of reaction curve, and Emmanuel&apos;s&apos; data for austenitic type 310 steel also suggest this type of solid state reaction. In addition, significant, though fragmentary, information has been given by Binder, Dulis and Smith,4 Payson and Savage,.; Guarneri, Miller, and Vawter,8 rerichs and Clark,7 Wilder,5 Lismer, Pryce, and Andrews,&apos; Smith, Dulis, and Link,10 Dulis, Smith, and Houston," and Henry, Cordovi, and Fischer." The bearing of these data on this work is covered in the discussion. The purpose of this paper is to present such correlated data on s formation in AISI type 304 (18 pct Cr-8 pet Ni), 347 (18 pet Cr-10 pet Ni-Cb), 316 (18 pet Cr-12 pet Ni-2 pet Mo), 309 (25 pet Cr-12 pet Ni), 310 (25 pet Cr-20 pet Ni), and 446 (27 pet Cr) stainless steels. Materials and Test Methods X-ray diffraction and metallographic methods were used to determine the first appearance of the s phase in cold worked filings and in annealed bulk samples of seven steels, under various combinations of time and temperature. The rate of growth of the s particles was not determined. Commercial heats of six AISI steels and a low carbon laboratory experimental heat containing about 28 pet Cr were studied. Analyses are given in Table I. Because cold work greatly accelerates the nucleation of s particles, the relative rates of s nucleation in mechanically strained samples, i.e., filings through 120 mesh, were determined for direct comparison with those in annealed bulk alloys of the same composition.

Jan 1, 1957

By R. W. Hyde, S. E. Eaton, B. S. Old

One of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects On both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steel-making. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2} The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2.3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States. It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaS04). The sulphur is subsequently found in the coke in combination with carbonaceous material of is composition and as calcium and iron sulphides&apos; In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke. Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two ""jar forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high .in total sulphur, would yield coke of fairly low sulphur content. Using the new

Jan 1, 1949

By R. W. Hyde, B. S. Old, S. E. Eaton

One of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects On both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steel-making. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2} The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2.3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States. It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaS04). The sulphur is subsequently found in the coke in combination with carbonaceous material of is composition and as calcium and iron sulphides&apos; In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke. Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two ""jar forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high .in total sulphur, would yield coke of fairly low sulphur content. Using the new

Jan 1, 1949