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By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By Charles Barron McIntosh

BECAUSE of the well known relationship between a low atmospheric pressure and increased amounts of methane in coal mines, attempts have been made to find associations between low pressures and coal mine explosions. An early study by F. Able disclaimed this relationship. He found that half the explosions took place during a rising barometer when methane content in a ventilated mine would be decreasing. A more recent study by C. L. Hosler revealed a close relationship between anthracite mine explosions and low atmospheric pressure. Bituminous coal mine explosions, where coal dust as well as methane can be exploded, were found to be more closely associated with a rising pressure following a low barometer than with the falling or low pressure period. Emphasis on rising pressure periods led the present writer to investigate the effect of the post-frontal or post-cyclonic weather on coal dust. Dust samples of uniform mesh were exposed in an Illinois mine. Analyses of the dust taken before and after the passage of cold fronts and their accompanying low pressure troughs indicated an increase in coal dust moisture prior to a frontal passage and loss of moisture from coal dust following the time of lowest pressure. Thus the warm, moist air (Tropical Maritime)found over the mine during the falling pressure period was cooled in the mine and moisture added to the dust. Cold, dry air (Polar Continental) accompanies' the rising barometer following a frontal passage and the air, being heated in the mine, subtracted moisture from the coal dust. A similar but seasonal phenomenon occurs from summer to winter, the dry dust period in winter being recognized as the more dangerous period. The question arose as to how the short period or daily changes in moisture content of coal dust compared with the seasonal changes. Temperature and humidity statistics were obtained from the surface and mine entry for the months of July andJanuary. The gain and Ioss of mdisture. to the hine were calculated for these two morths as were the gain and loss associated with mT (Tropical Maritime) and cP (Polar Continental),air masses as observed in the investigatiynsl. Temperature and humidity statistics tigatiynsl.taken from [the two air masses represent atimp span of only 34 hr. The redultant changes as presented in the accompanying table verify the supposition that short period changes in coal mine moisture may attain the magnitude of recognized dangerous seasonal changes. Statistics for the mT air and the July air have been placed next each other and those for cP and January air together for easier comparison of the two warm and two cold air units. The last column readily reveals that there is little difference in the amount of moisture being deposited in the mine from the mT air and the July average air. A similar conclusion is reached regarding the loss of moisture from the mine when it is affected by the cP air mass or the average January air. This comparison would be particularly true from late fall through early spring when strongly contrasting air mass changes are a common occurrence. The invasion of cold, dry air following a cold front thus produces a drying period that could well receive more attention as a danger period for coal dust explosions. This drying period would compare with Able's explosion period during a rising barometer. The drying period is also perltinent in Hosler's findings, where it was noted that the average explosion day (for bituminous coal mines) followed the day of lowest atmospheric pressure. Moreover, the author's investigation of some 365 coal mine explosions also indicates that this post-frontal period should receive special attention in connection with mine safety measures. Two comparatively recent major explosions in Illinois (Centralia and West Frapkfort) occurred after the mines had been under the influence of cold-dry air for 25 to 30 hr-following a deep low pressure passage. Dust was the important explosive element in both these explosions.

Jan 1, 1958

By S. T. Wlodek, John Wulff

Dense, adherent, and ductile coatings of chromium can be applied to Molybdenum by selectively freezing out the chromium solute from a supersaturated copper-or tin-rich liquid alloy. The successful exploitation of this technique depends on the control of variables common to any freezing process. Under the most favorable combimtion of supersaturation, nucleation, and mass-transfey, coatings as thick as 0.004 in. can be obtained. In exploratory experiments it was found that a coating of chromium may be applied to molybdenum by immersing the molybdenum body in a supercooled copper-chromium or tin-chromium melt and selectively freezing out the contained chromium onto the molybdenum body. Supercooling of the liquid metal plating bath can be achieved by cooling, or the maintenance of thermal or concentration gradients in the melt. The technique is similar to conventional dip-plating procedures where the sample is immersed in a molten bath of the pure plating medium, except that in these studies, the plating medium consisted of a dilute solution of chromium in liquid tin or copper. The success of this method requires that the base material to be plated be isomorphous with the coating and insoluble in the plating bath. In addition, the plating bath, while having an appreciable solubility for the coating component, must have negligible solid solubility in the solid plate. Such relationships exist in the molybdenum-chromium, chromium-tin, and chromium-copper systems. Liquid tin and copper are satisfactory as the plating solvent, because although chromium is appreciably soluble in both of these liquid metals, solid inter-solubility is almost negligible, and no compound formation occurs. The same relationships exist between molybdenum and copper or tin except that the solubility of molybdenum in liquid tin or copper is insignificant. It is this combination of solubility relationships, as well as the completely isomorphous nature of the molybdenum-chromium system, which allows the formation of a chromium coating on molybdenum by the selective freezing mechanism. Since the main deterrent to the widespread use of molybdenum for high-temperature structural applications is its poor oxidation resistance, the formation of a dense and ductile chromium coating on molybdenum may well be of commercial significance. In addition, the basic principle of coating formation by selective freezing should be applicable to other metallic or even nonmetallic systems. The precipitation of the solute from a liquid metallic solution, for the formation of a protective coating, has not been previously considered in the literature. Frequently, however, a similar phenomenon has been described in the corrosion of metallic heat exchangers by liquid metals1 wherein temperature gradients in the liquid metal heat-transfer medium result in the formation of layers or deposits of metallic residue2 in the cooler portions of the system. Impregnating techniques using liquid baths have been tried as a plating process. Semchyshen and Barr, for instance, have successfully diffused chromium into molybdenum by immersing the molybdenum specimen in a liquid tin-chromium or copper-chromium alloy. This simple holding technique fails to produce a layer of pure chromium and requires prolonged immersion to allow for the diffusion-activated enrichment of the molybdenum. During the course of this investigation, most of the phase relations published for the copper-chromium4 and molybdenum-chromium4 systems, were found reliable. It was necessary, however, to investigate the solubilities of chromium and molybdenum in liquid tin as well as the solubility of molybdenum in liquid copper. These determinations were made by a simpie weight loss technique on materials of the same purity as used in the plating studies. The results of these solubility studies are given in Tables I and I1 and indicate that although the solubility of molybdenum in liquid

Jan 1, 1961

By William L. Langdon

PRELIMINARY COMMENTS Recent years have been difficult for the mining industry, as reported in the most recently published Minerals Yearbook (Volume III), the estimated value of world crude mineral production has been generally declining since an historical peak in 1979 (16).* The costs of mineral extraction have, however, been rising rapidly. Individual project costs are, in general, exceeding the growth rate of mining companies, while operating and technical risks continue to increase (16). Risks resulting from currency flotation and political actions in the host country are also on the increase. Labor difficulties (such as those experienced by Phelps Dodge) and the Reagan Administration's recent rejection of a proposal by the International Trade Commission for higher tariffs and/or quotas on copper imports have also contributed to the mining industry's difficulties. The net result of these factors has been financial difficulties for mining companies with respect to paying for their current financial obligations as well as trouble finding new financing. It may be that one of the main factors in determining the future of the mining industry will be centered upon capital structure, i.e. how its assets are financed. Historical Perspective on Capital Structure In The Mining Industry As discussed by Isreal Borenstein in (4) and Thomas Navin in (7), mining firms typically have used a financial model based upon high financial leverage, i.e. large amounts of debt relative to equity. This has been especially true for American firms developing orebodies discovered overseas. Problems sometimes occurred for those who were forced to commit themselves to completion guarantees in order to obtain bank loans. Mines under these circumstances must be brought into operation regardless of market conditions. Politicians in overseas countries also may use the high profits required by these high risk ventures to argue for nationalization of mines. Coupled with the frequent use of high leverage, mining companies traditionally have paid out a higher percentage of earnings in the form of dividends than manufacturing firms. This is significant, in that such funds paid out in dividends are not available for other uses. Hence, a greater reliance upon debt and/or additional stock issues than would ordinarily be the case for manufacturing firms. Thomas Navin has stated in (7), that the theory behind the high dividend payout was that, "most mining investors thought of themselves as investing in a wasting asset, one that would gradually deplete over time until it ultimately became valueless." Investors, therefore, required a receipt, in the form of dividends, of a percentage of current earnings and a return on original capital. This view of reality, apparently, has not changed in some quarters, even though modern mine management ordinarily replaces depleted mines with new ones. It may be that this practice of high dividend payout coupled with relatively high financial leverage should be reexamined. Current capital structure theory could prove interesting and useful for those concerned with current conditions. Capital structure patterns and related practices in this industry are not, in many cases, congruent with those thought by some to be theoretically optimal. Prelude to Capital Structure Discussion With a few notable exceptions (such as the Guggenheims and Anaconda's chief operating,. officer in 1971) mining companies' chief executives and boards of directors have not been persons with financial backgrounds. This, one could conjecture, might have accounted for the relatively nonsophisticated nature of capital structures of mining companies. In order to appreciate the possibilities with respect to alternative influence on a firm's performance, one must be acquainted with the basics of financial theory. This paper is an attempt to familiarize the reader with (1) capital structure in general, (2) the usual components of this structure, (3) the general theory behind the use of financial leverage, and

Jan 1, 1985

By Nicholas J. Grant, Olaf Troili, John Chipman

IN recent studies of the factors which affect the rate of desulphurization and its equilibrium, it became apparent that certain concurrent reactions were operative which had a significant effect on desulphurization. This is emphasized in the experiments of Hatch and Chipman1 and of Grant, Kalling, and Chipman' by the slow approach to a final state of equilibrium which is in marked contrast to the initial rapid transfer of sulphur from metal to slag. Since the removal of sulphur is of such profound importance in iron and steelmaking, it appeared necessary to investigate the reactions responsible for this behavior. It is now known that the presence of iron oxide in the slag interferes seriously with the principal reaction of blast-furnace desulphurization: CaO (slag) +-S + C - CaS (slag) + CO [l] The interfering reaction is most simply expressed as: CaS (slag) + 0 = CaO (slag) +-S 121 and a small concentration of oxygen (or FeO) is sufficient to hold a considerable amount of sulphur in the metal. It has been shown by Grant, Kalling, and Chipman2 that the addition of MnO to blast-furnace slag slows the removal of sulphur from the metal. This effect overshadows the contribution of MnO to basicity and is ascribed to its oxidizing power. It will be shown in this paper that SiO, also has sufficient oxidizing power to interfere with blastfurnace desulphurization. This is, of course, only one of its several effects. Primarily it is an acid and therefore reduces the concentration of excess lime. But when silicon is reduced to the metal the oxygen to which it was previously bonded becomes in part available for reaction 2. The proof of this statement is found in the following experiments. Experimental Procedure and Results Utilizing the same procedure and apparatus described by Grant, Kalling, and Chipman' five additional heats were made using slags IV and 11, the starting compositions of which were: slag IV—40 CaO, 10 MgO, 35 SiO,, 15 A1,0,; and slag 11—50 CaO, 10 MgO, 25 SiO,, 15 Al3O3. An important difference between these heats and those previously reported was that silicon to the extent of 1 to 4 pct was added to the present heats whereas the starting silicon content was formerly about 0.2 pct. Table I shows the slag and metal analyses for heats 82 to 87, and Table I1 shows the silicon addi- tions made to the charge. These additions are based on 400 g of metal and 400 g of slag. All heats had 1.65 400pct S charged before the cold slagadditions. The temperature was maintained at 1525°C. Rate of SiO, Reduction: Fig. 1 shows the silicon content of the metal in contact with slag IV at 1525°C as a function of time. Heat 70 from the work of Grant, afunctionKalling,of and Chipman is included as the lowest starting silicon. It will be noted that eeven with 4 pct Si in the starting metal, there is an increase in silicon content with time. Heat 84 is apparently approaching silicon equilibrium very slowly. Heats 70 and 82 with very much lower slowly.starting silicon show a more rapid initial rise in startingsilicon content but do not reach equilibrium during a long holding period. Fig. 2 shows 3 different initial silicon contents for Fig.2shows3differentheats 73 (from Grant, Kalling, and Chipman) 86 and 87, in contact with slag II, the most basic slag. Heat 73 is increasing in silicon with time, whereas heat 87 with an initial silicon content of 3.7 pct shows a decrease with time. Heat 86 shows a very close approach to equilibrium. The rate of transfer of silicon from slag to equilibrium.metal is very slow in all of those heats, even those which are initially far from equilibrium. ____

Jan 1, 1952

By T. H. Butler

The two most talked of questions in the mining industry today are rock dusting and mechanical loading. The one as a matter of safety, and the other as a matter of economy, and both are of vital interest to the mining fraternity. Rock dusting and other safety methods will be dealt with by others at this meeting, so I will confine my few remarks to the matter of mechanical loading. I will not attempt to tell you what mechanical loaders are doing in the different mining fields throughout the country, or what they should do, but will endeavor to give you an outline of the work being done with mechanical loaders in No. 4 Mine of the Union Pacific Coal Company, at Hanna, Wye. In order that you may better understand and be in a position to follow me it will be necessary to cite the conditions under which we are working. and the type of loaders in use. The seam pitches from 14 to 17 degrees, and is normally 32 feet in thickness, and is overlaid with a soft sandstone roof. The panel system of working is used, planes being driven on the pitch, and rooms driven on the strike. Owing to faults being encountered planes are driven between the faults, and the. rooms on either side are in some instances 800 to 1,000 feet in depth. Rooms are advanced eight feet in height, and 32 feet in width, by hand loaders and .Toy mechanical loaders, and when driven to the boundary,, 18 feet of the remaining 24 is loaded out with Thew electric shovels, and six feet left to protect the roof. In January, 1916 the company installed a Type 1 Thew shovel, equipped with a 1 1/4-yard dipper, and in July, 1917, they installed a Type 0 Thew electric shovel, equipped with a 1-yard dipper, and in the year 1918 two additional Type 0 Thew shovels, equipped with a 1-yard dipper, were installed, making a total of four Thew shovels for this mine. The introduction of these shovels caused the employees much concern, and like all departures from the old methods of mining, met with indifference by some and open antagonism by others, so that for some time they results obtained were not satisfactory. However, by constant supervision and changes in the method of haulage the results obtained at present, while not entirely satisfactory, are much better and the production and costs are reasonably good. The Thew shovels in use are mounted on traction wheels with swivel axle and move. in all directions by their own power, and while the weight of each is approxi¬mately 20 tons, they are not as cumbersome as. one would think and are easily operated. The system used in working these shovels is to shoot the coal clown ahead of the shovels and maintain two tracks, two cars being used on each track so that shovel is loading on one track while driver is, changing cars on the other. When place is finished the shovel is run back to the first cross-cut by its own power and lowered to the next room with block and tackle, the roof coal in cross-cut being shot down to a height of 16 feet to allow passage of the boom. With better results from the Thew shovels we soon realized that it was necessary to find some method of developing rooms faster than was being done with hand loaders in order to keep the Thew shovels in working places, and in November, 1923, the company purchased from the Joy Machine Company two Type 4 B U Joy loaders, and the installation of same met with the same indifference and antagonism from the employees as did the Thew

Jan 1, 1924

By C. Gatlin, C. E. Nemir

A common cure of lost circulation is the introduction of granular bridging agents into the mud system. Many materials, such as ground nut shells, are used for this purpose. If the trouble causing void (fracture, fissure, vug, etc.) is not too large, the granular agent forms a "bridge" across or within the opening. Successively smaller particles in the mud stream then accumulate on and/or within this bridge until normal filtration is finally established. The efficiency of many bridging agents has been studied in the laboratory using various slot testers.',' Many investigators have remarked that a granular bridging material should have the proper particle size distribution. With the exception of the broad range specified in the patent of Goins and Nash,3 here is apparently no definition as to what this distribution should be. A bridge may be initiated when several particles of lost circulation material lodge against each other in a fracture or other void. Smaller particles then may bridge the openings between the larger, previously bridged particles. This process continues until the voids become quite small and the problem becomes one of filtration. It would seem logical that an optimum particle size distribution exists, i.e., one containing the proper quantity of properly sized material to fill the successively smaller voids of the bridge. The filtration characteristics of drilling fluids may be subject to a similar analysis. It has been clearly demonstrated by many workers that the filtration behavior of various muds can be altered by particle size control.'.' Slusser, et al, divided filtration into three periods and showed that particle sizes affecting a given period did not necessarily affect other portions of the filtration curve. An analagous problem is the proper sizing of gravel, liner slots and screen sizes in various sand-exclusion problems. Here the situation is reversed in that a proper "void" size, rather than the size of the bridging agent, is sought. The classic work of Coberly 9 forms the quantitative basis for most sand-exclusion processes. It is interesting to note that, in general, Coberly's work has been overlooked by most drilling-mud researchers. Other investigators have made various studies of the effect of particle size distribution .on drilling-mud properties. As a part of their studies, Fancher and Oliphant reported 30-minute filtration loss of a variety of mixtures of particle sizes.'' Gates and Bowie noted an effect of particle size distribution on filtration, as well as on other physical properties.' MAXIMUM DENSITY THEORY A maximum density mixture has been mentioned as the possible solution for both lost circulation and mud filtration problems. Furnas 12 derived mathematically a method for obtaining maximum density of beds of packed solids, having either a given number of component sizes or a continuous gradation of sizes. This work was verified experimentally by Anderegg.13 or mixtures having a continuous grading of sizes, the interval between sizes is taken as successive screen sizes of interval 2 The ratio of the quantity of each size and the next smaller size is given by the equation Fig. I, number of size intervals of ratio 2 taken from Furnas' paper, gives the value of n + 1 for any given values of + and K, where K is the ratio of the diameter of the smallest particles to the diameter of the largest particles. Measurement by weight assumes, of course, constant density for all particle sizes. Choosing the quantity of the smallest particle size as a unit weight, the required weights of the successively larger interials are then r1 r2 r3 . ®1,2,3. Thus, the grading curve of a maximum density mixture represents a geometric pro gression of ratio r.

By J. C. Yingling, J. W. Leonard

Introduction The absence of coal-face particle management heavily penalizes the transportation of coal from initial loading to final consumption. The penalties include dust problems, significantly reduced mine-loading-cycle productivity, mine-belt spillage, excessively high coal-preparation costs, chute blockages and dangerous pulverizer blockages at the final point of utilization. Fine particles commonly cause environmental and economic problems. It is well known that these fines can cause safety and environmental dust problems. But it is not well understood that these fines can also swell broken coal to a point where 5% to 15% more time and capacity must be used to deliver the same tonnage. In this paper, methods and rewards for reducing and/or managing fines at the mine face are discussed. Computer-based loading-cycle model productivity estimates, viewed from a new perspective, are made on the basis of material volume rather than on the long-established, and frequently misleading, basis of tonnage. It is typically the volume of broken material being transported that defines the capacity of a given transportation system, while the corresponding tonnages are merely a reflection of the specific material densities. Published evidence suggests that the swelling of broken coal can be decreased very significantly using small quantities of certain nonfrothing chemicals, which are added to mine-face spray water, and by employing improved mine-face breakage practices. In a future paper, the effects on transportation productivity beyond the coal mine will be discussed. The precursor to the work presented in this paper, involving the bulk density improvement for broken coal and the subsequent production gains for underground coal mines, was earlier presented in Leonard and Newman (1989). In the past, this topic has been studied and practiced only in byproduct coking in the steel industry. However, a potential exists for an increase in coal-industry productivity by improving the bulk density of coal to yield a subsequent reduction in delivered cost. This can occur with breakage, handling and treatment methods resulting in the loading of greater quantities of coal in fixed volumetric capacity haulage units such as mine cars, shuttle cars and scoops. Laboratory-based experiments to achieve an increase in productivity by increasing coal bulk density were discussed in Leonard, Paradkar and Groppo (1992). Chemical techniques using small quantities of commercially available reagents (surfactants) resulted in about a 13% to 15 % increase in bulk density, which was thought to produce a proportional increase in the productivity of a mine, together with a subsequent reduction in cost. The idea is to mix the reagents with the water that is used to spray coal during mining. In this paper, the impact of bulk density improvements on production rates is presented. Increases in production ranging from 60% to 88% of the bulk density increases are projected. This analysis was performed for atypical continuous-miner section. In the following sections, discussion and results of the analysis are presented. Discussion An analysis was performed to ascertain the impact of bulk density improvements on face-production rates for a typical continuous-miner section. Figure 1 illustrates the section layout and cut sequence. This layout and sequence is identical to the case described in King and Suboleski (1991). As can be seen, the section uses five entries and 12.2-m cuts that are taken by a remotely controlled continuous miner. The seam height is 1.5 m and two shuttle cars (5.7 t nominal capacity) are employed for haulage from the miner to the section feeder, which, throughout the cut sequence, is positioned as illustrated in Fig. 1. The simulation model was coded in the SIMAN simulation language. The major impacts of increased bulk density improvements on such a production system are as follows: •Shuttle-car payloads, in terms of the mass of coal transported per haul cycle, are increased proportionally to the increase in bulk density that results from the application of surfactant. •Shuttle-car discharge times should remain largely unchanged, because they are determined by the volume of material that is discharged, rather than the mass, and this volume does not change.

Jan 1, 1996

By H. H. Klepfer, M. E. Snyder

UNTIL very recently, the commercial availability of the rare earths as metals has been very limited. Fabrication of mill products from these metals has not been studied in most cases. This note reports the results of the development of fabrication techniques for thulium. Thulium has a melting point of about 1550°C and a hexagonal close-packed crystal structure. It oxidizes in air to give a black oxide (TmzO,). The procedures for producing thin thulium foil were developed on one ingot weighing about 220 g and were subsequently applied in processing about a pound of metal to foil. Several alternates for the various fabrication steps were investigated and will be discussed. The metal fabricated was in the form of commercial chill-cast ingots 1 in. in diam and 2 in. long weighing approximately 220 g. Impurities in the ingots were reported by the vendor to be 4000 ppni tantalum, 2000 ppm calcium, 200 ppm nickel, 100 to 200 ppm iron, 100 ppm europium, and less than 100 ppm copper, lutetium, and ytterbium. In addition to these impurities, several salt-like inclusions as large as l/8 in. in diam were revealed along the center line of the one ingot sectioned. Preliminary tests indicated that small wafers cut from the as-cast ingot would not fabricate readily by rolling. Forging of copper-jacketed wafers was therefore attempted. At 1550"F forging was satisfactory but an apparent reaction of copper with thulium demanded investigation of lower temperatures. Therefore, the remainder of the test ingot was forged at 1450°F—with only minor cracking. All ingots forged were inserted into copper tubes of 1 in. 1D and 0.125-in. wall thickness. The jackets were sealed by flattening the ends of the tubes and welding under helium. Heating time at 1450°F was 30 min. Press forgings of 1/8 in. per pass were used, followed by 10 min reheats. When the ingots had been squared and reduced to 0.250 in. in thickness, the original copper jacket was stripped off and replaced by a new jacket in preparation for hot rolling. Hot rolling at 1450" F without edge cracking was readily accomplished after forging. Excellent results were obtained with 10 pct reductions of thickness followed by 5 to 10 min reheats. After reduction of thickness from 0.250 to 0.100 in. the copper jacket was removed. It was found, in fact, that hot rolling in air was possible. A tenacious black oxide similar to that seen on zirconium was formed during 3 min reheats at 1450°F. Reduction in air to 0.010 in. foil was possible taking 10 pct reductions per pass. The oxide coat formed during hot rolling in air could best be removed by sand blasting and pickling. Common pickling solutions containing polar solvents were found to attack the metal too rapidly and a concentrated nitric-hydrofluoric acid mixture attacked neither the oxide nor the metal. The most satisfactory pickling solution was 52 vol pct concentrated nitric acid-48 vol pct glacial acetic acid. After forging to 0.250 in., vacuum annealing and cold rolling was found to be another satisfactory alternate to hot rolling in copper jackets. After forging. a hardness of Rockwell B76 was found. Annealing in vacuum (2 X l0-5 mm of Hg) for 1 hr at 1200"F did not alter this value. Annealing at 1470"F for 1 hr brought the hardness down to R;]63. With cold rolling (5 pct per pass) the hardness returned to about R,1:76 after 20 pct reduction and edge cracking became noticeable. However, cold rolling to a total of 40 pct reduction in thickness (RI,,83) was possible before edge crack propagation became serious. Good surface finish was obtained, and the metal loss due to oxidation was minimized by cold rolling and vacuum annealing. Using this procedure the yield of 1.25 in. wide by 0.010 in. thick foil from a 1-in. diam ingot was about 40 pct.

Jan 1, 1961

By J. A. M. Cano

Introduction Since the beginning of operations at the pellet plant at Ponta Ubu ES, Samarco Mineração SA has produced pellets for direct reduction and blast furnace processes. Of the total amount of pellets produced from 1977 through 1993, 55 % are used in the blast furnace, about 45 Mt (49.6 million st). The principal components of pellet gangue are calcium oxide, magnesium oxide, silica and alumina. They should be added in adequate quantities to guarantee the mechanical resistance of the fired pellets under blast furnace conditions. Over the years, the pellets produced by Samarco had a silica content between 2.5% and 2.8% and varying binary basicity preferably between 0.8 and 0.85. On the other hand, the increasing amount of industrial waste in siderurgical plants caused by the increase of steel production has caused some countries to put into practice methods to reduce the volume of slag produced in the blast furnace. This paper's goal is to find an alternative for decreasing the amount of slag produced in the blast furnace. It is possible to decrease pellet gangue by decreasing the silica content to about 2%, leaving the metallurgical properties and quality of pellets unaltered. For this work, Samarco pellets were used with Si02 between 2.5% and 2.8%, pellets with high silica and pellets with Si02 between 2.0% and 2.3% low silica. Both were partially fluxed by the range of varying basicity CaO/SiO2 from 0.8 to 0.95 during production. Experimental tests on pilot scale Thhis work began in January 1986 in the pilot plant (pot grate, Fig. 1) at Samarco. Its goal was to obtain preliminary data that would indicate the bybility of the project. It also formed a solid base to extend the studies in tests on an industrial scale of production for blast-furnace pellets. The pot grate is a test furnace composed of a gas burner, a combustion chamber and a grate, connected by hot air ducts. The burner is fed by a mixture of LPG and air. It reaches high temperatures through oxygen injection. The combustion chamber heats the air that comes from the turbocompressor. This hot air flows through the ducts to the grate on which the pellet samples are fired. During updraft drying, downdraft drying, preheating, firing and afterfiring, the upward and downward direction of the air flow can be controlled by valves driven by pneumatic cylinders. The pot grate indurator was fully automated in August 1989. Positive and negative pressures measurements resulting from gas passing through the pellet layer, as well as temperature readings, are recorded in graphs in relation to time for all tests. The tests depend on the various steps carried out in sequence that can influence the results of the tests. Therefore, some criteria were adopted to restrict the number of variables in the process. This was done to facilitate the results of the analysis. The pellets were composed of concentrate, bentonite, hydrated calcitic lime and metallurgical coal, all regularly used in the pellet plant. The material balance of the pellets mix was determined from the chemical analysis of the components. Table 1 shows the chemical characteristics of the concentrate and the additives used in the pilot plant and industrial tests. The basicity has a marked influence on the metallurgical properties of the pellets produced by Samarco with a silica content between 2.5% and 2.8%. However, for pellets with low silica (about 2%), it was necessary to study the variation in the parameters of quality in a wide range of basicities to deliniate with precision a scope of work. A large variety of low-silica blast-furnace pellets were produced at the pilot plant with binary basicity varying between 0.8 and 0.95. After chemical analysis, those pellets were separated into five groups of different binary basicity (0.8, 0.84, 0.87, 0.90 and 0.95). Each was then split, one part for metallurgical tests in the laboratory at Samarco and another to be evaluated in a laboratory for metallurgical tests in Germany. It was agreed that the tests to evaluate the quality of the pellets in the two [ ]

Jan 1, 1996

By Michael Hoch, Walter C. Wyder

The isothermul section of the Nb-Ti-Zr-O system at 1500°C was investigated using X-ray dzffraction and metallographic techniques. UP to 66.7 at. pct 0, the system contains nine four-phase regions. Tsopleths at 10, 20, 30, 40, 50, and 55 at. pct 0 weye constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of niobium, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct. O., PREVIOUS INVESTIGATIONS The Ti-Zr-O system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by anssen2 and Levin, McMurdie, and Ha11. Elliott4 has determined the Nb-O system by metallographic and X-ray diffraction techniques. He shows the existence of three oxides, namely NbO, NbO2, and Nb2O5. At 1500°C the solubility of oxygen in niobium is about 4 at. pct. No solid solubility region is shown for either NbO or NbO2. EQUIPMENT The same equipment as that for the study of the Ti-Zr-O system was used. The X-ray diffraction patterns were analyzed with the help of the ASTM card set5 and NBS circulars.6 MATERIALS The niobium powder (99 pct pure), the titanium powder (99.6 pct pure), the niobium pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmount Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., N.Y. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure," the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE Samples of the desired compositions were made up, in mole pct, from the materials listed above. In some cases the intermediate binary compounds, such as NbO and TiZrO4 were prepared beforehand and used in the preparation of the samples. This technique enabled equilibrium to be reached from two sides. The components of each sample were mechanically mixed in a mortar and pestle and pressed into 3/16-in. diam pellets. The pressures used in compacting were of the order of 50 to 100 x 103 psi. Sintering was accomplished by heating the samples in a tungsten crucible (3/4-in. high, %-in. diam, 1/8-in. wall, lid with XB-in. hole). The pellets were separated from each other and from the crucible by means of small spiral coils of tungsten wire placed between the stacked pellets and on the bottom of the crucible. The sintering time was from 4 to 12 hr at 1500°C under a vacuum of 6 x 101-5 to 1 x 10-6 mm of Hg. All samples were reground after the first or second heating repressed, and reheated. In most cases: equilibrium was obtained after the first heating, as the X-ray diffraction pictures after each heating remained unchanged. Quenching of the samples from 1500°C was at first only possible by allowing the crucible and its contents to lose heat by radiation. The temperature dropped from 1500° to 900°c in approximately 1 1/2 min, which was considered adequate when compared to the times used by other investigators to reach equilibrium in the temperature range of 1000°c and lower. Later, a new technique for faster quenching of the samples was cleveloped. This technique involved the removal of the samples from the crucible, whereupon they were quenched by coming in contact with the water-cooled copper base of the furnace. This manipulation was performed without breaking the vacuum. The sample pellets were placed on a tungsten wire rack inside the crucible. The wire rack passed through the hole in the crucible lid, where it was connected to a small nonmagnetic chain. The chain was fed to the side of the furnace by means of a brass rack which fitted between the body and lid of the furnace. Suspended at the end of the chain, near the furnace wall, were three magnetic washers. With the use of a strong

Jan 1, 1962

By John Crusius

? 3-year research program overview ? initial results- MainZone pit Waterline pit ? questions raised ? increasingly common in western N. America ? frequently low-pH waters with elevated concentrations of many metals ? water quality controls poorly understood ? some in U.S. are Superfund sites

May 1, 2002

By William Gleason

During a mining roundtable at the U.S. Department of State on Aug. 7, President Donald Trump announced that the U.S. Government will invest $3 billion in critical minerals and battery projects as part of a push to increase domestic production, boost national security and support industrial policy. Part of this investment includes $180 million earmarked for education and workforce development for the mining sector, including up to $100 million to strengthen education in critical minerals and materials from the U.S. Department of Energy (DOE) and $80 million from the U.S. Department of War (DOW) for investments in the Colorado School of Mines, South Dakota School of Mines and Technology and Johns Hopkins University. The DOE’s Office of Critical Minerals and Energy Innovation (CMEI) announced a notice of intent for up to $100 million to develop a new program called “Providing Opportunities for Specialized Education in Critical Technologies (PROSPECT).” The DOW investment will be used to build technology innovation hubs, form projectfocused partnerships between students and defense industry, develop new processes and prototypes, and certify hundreds of new students with advanced degrees in mining, geology and metallurgy. Department heads from the 14 ABETaccredited mining schools in the United States attended the meeting held at the Department of State. They were joined by Trump, Secretary of State Marco Rubio, Secretary of the Interior Doug Burgum and Secretary of Commerce Howard Lutnick as well as several industry leaders including James Litinsky, chief executive officer of MP Materials; Vicky Peacey, president of Resolution Copper; Robert Friedland, founder of Ivanhoe Mines; Mitchell Krebs, chief executive officer of Coeur Mining as well as representatives from Rio Tinto, BHP, Energy Fuels and a number of other industry leaders. “I am not aware of another time in history when the leaders of the U.S. mining education community have been brought together with a sitting President, Cabinet officials, and industry leaders to discuss the future of American mining,” said Aaron Noble, Charles T. Holland Professor Department Head - Mining and Minerals Engineering and interim department head - Materials Science and Engineering at Virginia Tech. “Mining education was not on the periphery of the conversation; we quite literally had a seat at the table where national mineral strategy was being discussed. I hope we look back on this as an inflection point for American mining education.” The historic funding announcement comes in response to a critical need for more mining and processing engineers in the United States. The DOE estimates the industry will need 6,000 more mining engineers during the next decade. Noble said U.S. programs currently graduated fewer than 200 mining engineering graduates annually. Meeting that demand has been a challenge for many years. Enrollment in U.S. mining programs has declined by approximately 45 percent since 2015, and data compiled by the Society for Mining, Metallurgy & Exploration (SME) and the Society of Mining Professors show enrollment falling from nearly 1,500 students eight years ago to fewer than 600 in 2023. The investments offer the 14 mining schools an opportunity to expand enrollment, modernize curricula, strengthen industry relationships and build a more stable workforce pipeline. Kray Luxbacher, executive director and head of the University of Arizona School of Mining Engineering and Mineral Resources, attended the roundtable. She said mining school department heads across the country are “fighting to grow enrollment to meet industry demand.” “This funding is an opportunity to change the trajectory of mining,” Luxbacher said, “to bring in students who didn’t grow up around mining, show them what a modern career in this field looks like and give our programs the resources to compete for their attention.”

Sep 1, 2026

By P. R. Smith, R. A. Walters

Borates have been mined in the desert areas of California and Nevada for more than 100 years. To about 1890, playa surface mining provided the chief sources of boron minerals. Underground mining of colemanite and later of borax and kernite was predominate until about twenty years ago. Open pit mining of the large deposits of borax and kernite near Boron, California has been most significant for the past twenty years. Mining of colemanite in the Ryan, California area, near Death Valley, began in 1907. Following the discovery of the large deposits in the Boron area (about 1957), mining in the Death Valley area became nearly nonexistent. Only small tonnages were mined for special uses. Little mining was done in the Boraxo area near Ryan. The first claim was made in about 1915. In 1960 the area became the property of the Kern County Land Company, which was acquired by Tenneco Oil Company in 1967. In 1976 the various boiate properties and claims in this region were acquired by American Borate Corporation. The open pit mine is now approximately 122 m (400 ft) deep, 910 m (3000 ft) long and 305 m (1000 ft wide). The borates in the Boraxo pit consist primarily of three minerals. These are about 50% colemanite (CB6011 5H20), about 40% probertite (NaCaB50g 5H20), and 10% ulexite (NaCaBgOg 5H20). The colemanite, along with boric acid and high-grade colemanite ore from Turkey provide the only sodium-free borates for production of textile grade fiberglas. When heated to its decomposition temperature, colemanite decrepitates to a fine powder, which is the basis for the concentration process. The gangue minerals in this deposit are primarily calcite and clays, including bentonite. The ore body has a very low arsenic content, which is a desirable feature. Test work had been done with samples prior to the results discussed herein. This paper will discuss results of test work which were the basis for erection of a plant, and the subsequent plant operations. Laboratory Calcination and Air Tabling Tests Laboratory calcination tests showed that substantial upgrading of the borate could be accomplished by calcining followed by screening of the calcined material. Removal of the + 28 mesh calcine resulted in borate losses of less than 10% with a rejection of 40 weight % or more of the calcine. The minus 65 mesh calcine generally met the requirement of containing 48%, or more, B203. The minus 28 plus 65 mesh material contained an intermediate quantity of borate and would require additional treatment. Testing demonstrated that ore would not have to be reduced to a size finer than 19 mm (3/4 in.) prior to calcination. A temperature range from 400 to 455OC (750 to 850°F) was apparently satisfactory. Calcination at a temperature of 48Z°C (900°F), or higher, was unsatisfactory due to fusion. All laboratory calcination tests were static tests conducted by placing small covered charges in a laboratory furnace for 40 min. In all tests vapor issues from the furnace for 5 to 7 min. Following this period the ore could be heard "popping," due to decrepitation of the colemanite. The reaction generally continued for approximately one-half hour. Various size fractions of the calcination products from laboratory tests were subjected to laboratory air tabling tests, usually after removing the plus 28 mesh material. Laboratory air tabling tests were conducted employing a Whippet V-80 model air table manufactured by Sutton, Steele and Steele Co. now known as Tripple S Dynamics. Variables include both end and side-tilt, speed of vibration, and quantity of air rising through the deck. In addition to the variables in the machine itself, the feed rate is also a rather critical variable. Testing demonstrated that all - 28 mesh size fractions of the calcine could be successfully concentrated to 48% F2O3 or greater. For the finer material recoveries into the concentrate were between 85 and 90% of the borate. With the coarser material a substantial amount of middling was produced which required cleaner tabling. Laboratory calcination and air tabling tests indicated a process whereby the borate could be concentrated to about 50% B203 with borate recoveries approaching 90%. Moreover, the iron content of the concentrate was well below the required specification of 0.3% Fe2O3. Pilot Plant Calcination Following the laboratory test work described above, pilot plant testing was conducted to prove the process, provide data for engineering studies, and provide product for a prospective purchaser. The kiln used was 0.9 m-diam (3 ft) by 9.0 m (30 ft) long and had a belly section 1.2 m-diam (4 ft) by 2.74 m (9 ft) long near the discharge end. The kiln was operated at a speed of 0.7 rpm. Gas was fired into the kiln at an average rate of 27.1 m3/hr (958.4 cu ft per hr). The air to gas ratio used was 10:1. The ore was fed to the kiln countercurrent to the flame and discharged through a hopper into a screw conveyor which discharged to a 1.2 m (48 in.) Sweco separator. The separator had 28, 65, and 150 mesh screen cloths, with the plus 28 mesh fraction being discarded. The minus 28 mesh fractions were later subjected to air tabling. The exit gases, containing some calcine dust, were swept through two cyclones to recover the dust. The gases then were scrubbed in a Ducon scrubber; very little dust reported past the first cyclone. The dust from the first cyclone was also saved in drums. In addition to the gas rate, the flue gas velocity, after

Jan 1, 1981

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

By E. J. Nielsen, P. R. Strutt

A study has been made of the progressive changes in the distribution of etch-pit structures occurring during high-temperature creep in copper + 7 wt pct Al single crystals oriented with a [113] tensile axis. The two equally stressed glide systems with the highest Schmid factor would be expected to form subboundaries of the type predicted by Kear.2 The alignments of etch-pits on sections parallel to different (111} planes consistent with these types of boundaries were not observed. However, they were consistent with planar subboundaries (on a macroscopic scale). From an analysis of Amelinckx1 it may be shown that stable cross-grid dislocation boundaries may form in the primary slip planes. These boundaries form when dislocations with a Burgers vector not in the slip plane move into the plane by combination of climb and glide. THE geometry of subboundaries formed by the interaction of dislocations of two glide systems has been analyzed by Amelinckx,1 and the particular types produced by deforming fee crystals are predicted by ear.&apos; In this paper types of boundaries which may be formed when climb as well as glide occur are discussed as this is relevant in high-temperature creep. It is assumed in the present investigation that the etch-pits observed in Cu + 7 wt pct A1 on surfaces parallel to {111} planes delineate the sites of dislocations. Although there is no direct evidence for this previous work on a-Cu/Al single crystals by Mitchell, Chevrier, Hockey, and Mon-aghan,3 would show this assumption to be reasonable. The alignments of etch-pits which form during creep are studied on sections parallel to each {111) plane. It is then deduced that these alignments are consistent with a specific type of planar subboundary. The Cu + 7 wt pct A1 single crystals had a [113] tensile axis and Fig. 1(a) shows schematically the relation of the slip planes and slip directions (as represented by tetrahedron ABCD) with reference to the tensile axis. The two equally stressed glide systems with the maximum Schmid factor namely ß-AD and (a-BD, from the analysis of Kear,2 would be expected to form the boundaries shown in Fig. l(a) and (b), also Fig. 5(a) and (b). EXPERIMENTAL PROCEDURE The a-Cu/Al single crystals were grown and annealed in a "gettered" argon atmosphere. Chemical analysis showed the aluminum content to be uniform in each crystal and the difference between crystals was maintained to an accuracy of ± 0.25 wt pct. The initial dislocation density and mean subgrain diameter after annealing was -106 cm-2 and 250 µ, respectively. Surfaces parallel to (111) planes were produced by specially developed electrolytic machining processes. The {111} faces were next electropolished for 5 min in a solution consisting of 25 g chromium trioxide, 113 ml glacial acetic acid and 40 ml water; the applied potential was 8 v. Dislocation etch-pits were revealed using l an etchant described by 1 ml bromine, 45 ml HCl, and - 250 ml water. RESULTS In crystals strained into secondary creep at higher stresses (443 and 750 g - mm-2 at 650° C aligned rows of etch-pits parallel to slip plane traces were evident in sections parallel to the (1111, (ill), and (111) planes, see Fig. 3. As well as the longitudinal alignments in Fig. 3, well formed randomly oriented arrays indicative of an equiaxed subgrain structure are evident. At the lower stresses (100 to 230 g . mm-2) only an equiaxed structure formed during creep. The sections in Fig. 3 are from a crystal crept for 70 hr at 650°C with a CRSS of 443 g.mm-2. Two identically oriented crystals were also deformed at the same temperature and stress for 5 min and 4 hr. In the crystal crept for 5 min, the etch-pits were randomly distributed with no tendency for directional alignment, see Fig. 2(a). As shown in Fig. 2(b) aligned arrays were evident after 4 hr creep but they were not nearly so well defined as in Fig. 3. The alignments (parallel to the arrows) in Fig. 3 are consistent with the existence of boundaries in the two main slip planes a and ß. The way in which this is deduced is seen by reference to Fig. l(c), where the existence of boundaries in the a and ß planes is verified by sectioning parallel to a,ß, and d. The (111) and ß(111) planes intersect the d(111) plane along BC [101 ] and AT [011] and alignments parallel to [101] and [011] are clearly evident in Fig. 3(c) in a section parallel to the d(111) plane. Similarly the a, and ß planes in Fig. l(a) intersect each other along DC [110] and hence there will be an alignment parallel to [110 ] in sections parallel to the a-plane and the ß-plane; this is evident in Fig. 3(a) and Fig. 3(b). It is interesting to note that alignments of etch-pits consistent with the boundaries predicted by Kear2 were not observed; see Figs. l(a) and l(b). The geometry of boundaries in {111} planes as shown in Fig. l(c) is discussed later. In Fig. 4(a) the individual etch-pits are resolved and the alignments are exactly parallel to the slip trace direction [101]. However, in some areas alignments deviate away from the slip trace direction by as much as 10 to 15 deg, this is evident in Fig. 4(b), and in Fig.

Jan 1, 1969

By G. R. Speich

The distribution of carbon and the type of substructure in iron-carbon martensites containing 0.02 to 0.57pct C has been studied in the as-quenched condition and after tempering at 25" to 700°C by using electrical resistivity, internal friction, hardness, and light and electron microscope techniques. in marten-sites containing less than 0.2 pct C, almost 90 pct of the carbon segregates to dislocations and to lath boundaries during quenching; in martensites containing greater than 0.20 pct C, appreciable amounts of carbon enter normal interstitial positions located far from defects. Tempering martensites with carbon contents below 0.20 pct at temperatures below 150°C results in additional carbon segregation to dislocations and to lath boundaries but no carbide precipitation whereas -carbide precipitation occurs in martensites with carbon contents exceeding 0.2 pct. Above 150°C, a rod-shaped carbide (either Fe3C or Hagg) is precipitated in all cases. At 400°C, spheroidal Fe3C precipitates at lath boundaries and at former aus-tenite grain boundaries. At 400" to 600"C, recovery of the martensite defect structure occurs. At 600" to 700°C, recrystallization of the martensite and Ost-waW ripening of the Fe3C occur. The effects of the carbon segregation that occurs during quenching and the subsequent substructural changes that occur during tempering on martensite tetragonality, hardness, and precipitation behavior are discussed. A mathematical analysis of carbon segregation during quenching is presented. RECENT studies of the strength of low-carbon martensitel-4 emphasize the importance of carbon segregation to the martensite lath boundaries and to the dislocations contained between them during quenching. Unfortunately, very few studies of the tempering of low-carbon martensites have been conducted, so the exact nature of this segregation is poorly understood. In fact, most early tempering studies5,6 were restricted to carbon contents greater than 0.20 pct. Moreover, these studies did not determine the amount of carbon segregated to the martensite substructure during quenching so that the initial state of the martensite was not established. Aborn7 studied the precipitation of carbide in low-carbon martensite during quenching but did not establish whether carbon segregation occurs prior to carbide precipitation, nor did he study the subsequent tempering sequence in detail. In the present work we have used electrical resistance and internal friction measurements, supplemented by electron transmission microscopy to establish the carbon distribution in as-quenched specimens. Specimens thin enough to avoid carbide precipitation (but not carbon segregation) were employed. The redistribution of carbon on subsequent tempering below 250°C was followed by measurements of elec- trical resistance. Additional studies were made on specimens tempered at 250" to 700°C to elucidate the overall tempering behavior of low-carbon martensites, including the formation of cementite and recrystalli-zation of the martensite. EXPERIMENTAL PROCEDURE Eight iron-carbon alloys with 0.026, 0.057, 0.097, 0.18, 0.20, 0.29, 0.39, and 0.57 wt pct C were prepared as 8-lb ingots by vacuum melting. Typical impurities in wt ppm were 40 Si, 20 Mn, 30 S, 10 P, and 10 N. These alloys were hot rolled to 3 in. plate at 1095°C) (2000°F). The hot-rolled plates were surface ground to remove scale and the decarburized layer, then cold rolled to 0.010 in. sheet. Specimens cut from the sheet were austenitized for 30 min at 1000°C (1830°F) in a vacuum tube furnace in which the pressure did not exceed 2 x 10-3 torr. Chemical analysis of specimens after austenitization indicated no decarburization at this pressure. Immediately before quenching, the furnace was filled with prepurified helium. The specimen was then pushed rapidly through an aluminum foil gasket, which sealed the bottom of the furnace, into an iced-brine bath (10 pct NaC1, 2 pct NaOH). The quenching rate at the M, temperature is about 104&apos;c per sec for 0.010 in thick specimens, as calculated from Newton&apos;s law of heat flow2 using a heat transfer coefficient of 25 ft-&apos;. This quenching rate is sufficiently high so that all the alloys transformed completely to martensite throughout the entire 0.010 in thickness and no carbide precipitation occurred in the martensite. All specimens were immediately transferred to liquid nitrogen after quenching and stored there until needed. Tempering below 250°C (480°F) was done in silicone oil baths thermostatically controlled to *;"C. Tempering above 250°C was done in circulating air furnaces or lead pots with the specimens contained in evacuated silica capsules. Electrical resistance was determined by measurement of the potential drop across both a standard resistance and the specimen, connected in series. All resistance measurements were made in liquid nitrogen (77K, -196°C) to minimize thermal scattering of electrons and thus maximize the contribution of impurity scattering to the resistance. Specimen dimensions were 5.10 by 0.19 by 0.025 cm. Although the precision in the electrical resistance measurements was +0.1 pct, the electrical resistivities could only be measured with an accuracy of +5 pct because of uncertainty in the specimen dimensions. Internal friction measurements were performed in an inverted pendulum apparatus at vibration frequencies of either 1.9 or 66 Hz. The specimen dimensions were 5.10 by 0.375 by 0.025 cm. Hardness measurements were made with a Leitz-Wetzlar microhardness machine with loads of 100 g. Specimens were examined by light microscopy after etching in 2 pct Nital and by electron transmission microscopy after preparation of thin sections by electrolytic thinning in a chromic-acetic acid solution.

Jan 1, 1970

By T. E. Evans, C. T. Baroch

ZrB2 was produced in batches of 4 to 6 Ib by interaction of ZrO2, B4C, B203, and carbon at around 2000°C in a simple graphite resistance furnace. Techniques of production are discussed and the final design of a suitable furnace is described in detail. Several other borides were made by the same technique and the process appears to have possibilities for commercial production. N seeking out new hard and refractory com- pounds, many researchers have turned to the investigation of the borides and excellent papers have been published on the properties of these compounds. Few papers, however, have appeared on the techniques and problems concerned with the production of these high temperature substances. This report describes progress made in developing a method for preparing zirconium diboride, ZrB2, on a pilot plant scale. The literature of the borides and other refractory hard metals recently has been reviewed, annotated, and classified so completely&apos; that it is needless to attempt such an outline here. It is enough to say that three borides of zirconium have been reported: ZrB, ZrB2, and ZrB12.2 ZrB2 is the most stable of these and is especially stable in the presence of carbon up to and including its melting point of around 3000°C. Like most borides, it can be prepared in several ways. It can be prepared by synthesis of the elements, but these are expensive and difficult to produce in a high state of purity. Obviously, production directly from the oxides would have decided economic advantages. In electrolytic production such as that of calcium boride,:&apos; the product is recovered as a sludge mixed with electrolyte; and separation of product from adhering electrolyte and regeneration of the electrolyte is an involved and difficult process. The work on borides was started on a small scale in 1948. Late in 1949, Naval Ordnance expressed a specific interest in ZrB2 and the project then centered on this compound. After the usual experimental work necessary in a new field, ZrB2 of good quality was produced by heating mixtures of B4C, ZrO2, B2O3, and carbon to a temperature of about 2000 °C in a resistance-type electric furnace. Over 100 lb was made for experimental use tests, and the method of production probably could be expanded into a commercial operation. A similar process has been described by Kieffer and coworkers.&apos; The main chemical problems were the development of proper charges to insure complete reduction of the elements, determination of the proper temperature range at which these reductions took place, and adoption of techniques necessary to pre- vent inclusion of such impurities as carbon and nitrides. The mechanical problems consisted of developing a simple practical furnace that would attain the high temperatures required and permit use of a controlled atmosphere when necessary and determining of suitable refractories. Both problems were solved by designing a crucible resistance furnace. Crucible Resistance Electric Furnace Attempts were first made to produce ZrB2 in an electric arc furnace, but such a furnace would not provide the degree of carbon control required for producing clean graphite-free borides, so it was decided to try working in a crucible. Obviously, the furnace would have to be constructed of graphite, as the temperatures required are too high for other refractories or heating elements. Crucibles were made by hollowing out segments of graphite electrodes, which were fitted with a cover and clamped between two electrodes so that the current passing through the thin wall of the crucible would generate heat, using the principle of the Helberger crucible furnace."? Preliminary tests with this type of furnace were encouraging and led to the furnace design shown in Fig. 1. The essential components were a thin-walled graphite crucible resting on a graphite block, which formed the lower electrode assembly, and a top electrode assembly swung from a pipe column making contact with the top of the crucible. The space around the crucible was filled with graphite prepared from waste electrodes crushed to about ¼ in. This packing had excellent insulating properties, both electrically and thermally, and could be removed easily and quickly from around the crucible by means of an industrial vacuum cleaner. The largest resistor crucibles were machined from 8 in. electrode stock and were 26 in. long, with a side wall Yi in. thick and a 1 in. bottom. Temperatures were determined optically by sighting down a 1 in. hole drilled longitudinally through the top electrode and the crucible cover. Sealing this hole at the top was a water-cooled brass sight-glass assembly, shown in Fig. 2. An opening was provided for a light flow of helium to keep the sight opening clear of smoke, and a glass prism above the sight glass changed the line of sight to the horizontal for easier reading. More recently, the prism and optical pyrometer were replaced by a photoelectric recording pyrometer. At first the charges were placed directly in the resistor crucible but this meant that everything had to be withdrawn from the furnace every time the charge was emptied. Later, smaller crucibles were made up that could be placed inside the resistor

Jan 1, 1956

Jan 1, 1936

Jan 1, 1936