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By R. V. Wheeler, W. Francis

Of the methods that have been used for studying the chemical composition of coal, attack by reagents has not, in general, yielded much information. Most of the reagents used have been strong oxidants such as nitric acid or Schulze's solution. The use of a milder oxidizing agent, such as air at low temperatures, enables progressive changes in the character af the coal substance to be studied and thus helps toward an understanding of its constitution. British bituminous coals frequently have a banded structure. These bands (of four types) can be separated one from another and have been found to possess markedly different chemical characteristics, even when taken from contiguous portions of the same lump coal. It has been found convenient to give each of the ingredients of banded coal a distinctive name, more or less descriptive of its appearance, and the study of the chemistry of bituminous "coal" in England has resolved itself into a study of each ingredient separately. The coal chosen for this work was taken from the Top Hard seam at East Kirkby colliery, Nottinghamshire, a detailed chemical analysis of which has been recorded by Baranov and Francis.' The banded structure was well marked and the bands could readily be separated. The research was confined to the brilliant vitreous bands (vitrain), the dull hard bands (durain) and the "sooty partings" main); for previous work had shown that the fourth type, to which the name clarain has been given, is intermediate in character, chemically, between vitrain and durain. The method of experiment was, briefly, to draw a slow current of moist air through weighed samples (50 gm.) of the three ingredients, vitrain, durain, and fusain, in the form of powder (through a 60-mesh and on a 90-mesh sieve) contained in glass tubes which could be maintained at a constant temperature during prolonged periods. After passing through the coal, the air bubbled into a measured volume of

Jan 1, 1925

By Michael Hoch, Walter C. Wyder

The Cr-Ni system was investigated between 900" and 1400°C and 45 to 100 wt pct Cr. The Cr-Fe system was studied between 1200" and 1385°C and 70 to 100 wt pct Cr. Powdered alloy compacts were produced from high-purity chromium, nickel, and iron poulders. The compacts were sintered in an argon atmosphere and then machined into small, 0.030-in. diam cylindrical specimens. These were then heated by induction in the high-temperature X-ray diJfractwn camem under a helium atmosphere and irradiated with copper Ka radiation. From the results of the high-temperature X-ray diffraction patterns it can be concluded that chromium exists only in the bcc form, and that no eutectoid reaction occurs in the Cr-Ni system in the temperature interval 900" to 1400°C. The X-ray diffraction patterns are in agreement with the Cr-Ni phase diagram of Bechtoldt and Vacher, and Williams. It is possible that chromium undergoes one or more allotropic transformations between room temperature and its melting point. Most of the evidence was gathered from the study of the chromium-rich ends of the Cr-Ni and Cr-Fe binary systems. All the investigations rely heavily on indirect methods: thermal analysis, electrical resistivity, and micro-graphic inspection of quenched samples. In the present work the chromium-rich side of the Cr-Ni and Cr-Fe binary systems is studied, using high-temperature X-ray diffraction techniques. Thus the coexistent structures can be observed directly at temperature. PREVIOUS INVESTIGATIONS ~ansenl shows two possible Cr-Ni phase diagrams 1) a simple eutectic [Liquid =a-Cr(bcc) + y-Ni(fcc)], 2) a eutectic [Liquid+ P-Cr(fcc) + y-Ni(fcc)] and euctectoid [p-Cr(fcc) ==a-Cr(bcc) + yNi(fcc)]. The latter is based on the work of Grant and co-workers.2 Stein and rant'" placed the eutectoid composition at 1215°C and 68 wt pct Cr; their diagram is shown in Fig. l. Similarly, Sully3 also discusses the two proposed diagrams. Price and Grant,4 working on an isothermal section of the Cr-Ni- Fe ternary diagram at 1300°C, made no mention of a ß-chromium phase (fcc). The ß-chromium structure was also reported by Misencik 5 in the Cr-Nb(Cb) system. Williams 6 studied the Cr-Ni system using precipitation techniques. His work included the chromium and nickel solvus lines below 1250°C. He reported no ß structure nor any eutectoid reaction. The solvus lines which he produced were very similar to those of Jette, et al 7 below 1000°C. He concluded that Grant and coworkers2 had misinterpreted their data, and that effects which they had reported were actually due to the rapid and extensive precipitation of the nickel-rich phase. Bechtoldt and vacher8 used sintered powdered alloy compacts in an attempt to find the ß phase. They used metallographic and room-temperature X-ray diffraction techniques and also failed to detect the fcc chromium phase. They attributed the low slope of the chromium solvus at approximately 1150°C as the probable cause of the abundant precipitation obtained. They also stated that the precipitation was the probable cause for the abrupt discontinuities in the thermal analysis and electrical resistivity data which led to the conclusion that a eutectoid reaction existed. Fig. 1 also shows their diagram. Grigor'ev and coworkers9 investigated the polymorphic changes of chromium in the Cr-Ni phase diagram. Using standard microstructural and thermal analysis techniques, they published a phase diagram which contained five polymorphic forms of pure chromium and four eutectoid reactions. They stated that the room-temperature bcc chromium transformed to a fcc structure at 930°C, to bcc at 1300°C, to hcp at 1650oC, and then finally to bcc at 1830°C. The eutectoid reactions were placed at 850°, 960o, 1140°, and 1220°C. Also to be noted was the fact that the uppermost phase, the bcc above 1830°C, was different from the upper phase of Grant and coworkers,2 the fcc above 1840°C. Their eutectoid reactions, temperatures and compositions fall

Jan 1, 1963

By H. L. Marcus, C. D. Turk

Titanium was physically vapor-deposited by electron beam high rate evaporation. Rates of 50,000 and 85,000Å per min at deposition temperatures of 480°, 535°, and 595°C were used. Deposited thickness ranged front 0.004 to 0.010 in. The evaporated titanium had a high degree of basal Plane texture. The specimens were tested in tension at temperatures ranging from 78° to 520°K. From the data, the yield stress, thermal component of the yield stress, and work hardening characteristics were found as a function of temperature, deposition rate, and deposition temperature. It was found that Taylor's equation, best fit the work hardening data with m = 1/2. MANY investigations have been made on the tensile deformation characteristics of commercial- and high-purity titanium.1"7 The data obtained from these experiments emphasize the fact that the mechanical properties are generally related to the method of production. The correlation of mechanical properties to production history arises from the dependence of impurity concentration on the extraction and melting technique used. Additional effects are derived from crystallographic texturing which can result from fabrication history. Lee and Backofen8 and other investigators9 have shown that crystallographic texturing in titanium sheet has a significant effect on the deformation characteristics. Bunshah and Juntz10 prepared high-purity titanium by high rate physical evaporation techniques. These authors found the deposited material to have a columnar structure with grain sizes ranging from 12 to 104 µ, depending upon the substrate temperature. The room-temperature strengths of the coarse-grained distillate were similar to arc-melted, rolled. and annealed crystal bar titanium. Commercial-purity titanium was also produced experimentally in our laboratory using high rate physical vapor deposition techniques. The commercially pure material has a finer structure than the high-purity distillate,10 and is highly textured. Since the method of preparation and degree of texturing affect the mechanical properties, a research program was initiated to determine the temperature dependence of the yield stress and work hardening characteristics as a function of high rate deposition parameters. This paper relates the results of the investigation. EXPERIMENTAL A) Material Preparation. The titanium was received in the form of commercial-grade 0.096-in.-diam wire which has a composition of 0.016 pct C, 0.0037 pct N, 0.110 pct 0, 0.011 pct H, 0.05 pct Mn, 0.051 pct Fe. balance Ti. The wire was continuously fed into a vacuum evaporation unit as shown schematically in Fig. 1. The deposition chamber was evacuated, purged with argon, and reevacuated to a pressure of 10-5 Torr which was maintained during deposition. A focused electron beam was used to evaporate the titanium from a water-cooled copper crucible. The titanium vapor was condensed onto a preheated titanium substrate. The temperature of the substrate was controlled within ±5°C for the deposition temperatures of 480°, 535°, and 595°C. Control of the input power enabled the use of two deposition rates. 50,000 and 85,000Å per min. The evaporated titanium had a final analysis similar to that of the input titanium, within experimental limits. B) Testing. The evaporated titanium was physically stripped from the titanium substrate and machined into tensile specimens with 1-in. gage lengths. In addition, tensile specimens of as received annealed 35-A titanium sheet with a 20 µ grain size and 45 pct cold-rolled 35-A were also prepared. All specimens were tested in tension in an Instron at a strain rate of 3.3 x 10"4 in. per in. per sec. Proportional limit has been used as a measure of yield strength. Tests were conducted at 78°, 220°, 300°, and 520°K. Metallography, X-ray diffraction, and electron microscopy were used to correlate structure with the deposition parameters and mechanical properties. Room-temperature X-ray measurements were made to determine the phases present. Pole figures and a scans were made to determine deposition texture. Because the vapor deposition was symmetrical about the normal to the substrate, there was no preferred di-

Jan 1, 1969

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine' who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H'-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson'28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By R. J. Linney

Reserve Mining Co. produces 5 million tons of iron ore pellets per year. The finished product runs about 65.50 pct Fe, with 7.75 to 8.00 pct SiO2. Less than 12 pct arrives at the blast furnaces smaller than % in. This plant was originally designed to produce 3.75 tons annually—not 5 million. To handle the increased tonnage a fifth fine crushing line was added, and some very minor changes were made. When production can be stepped up 33 1/3 pct without extensive additions or changes—within the short period of a year—basic engineering has been sound. Operators of the plant consider it the best design job they have seen or heard of, and competent authorities have said that start-up was quicker and easier than for any previous large-scale minerals beneficiation plant. One big advantage is the elbow room allowed. Generally speaking, there is an eternal conflict between operator and designer over space. The designer has his costs per cubic foot, and he is keenly aware that if he permits the number of cubic feet to rise unnecessarily, total costs will be too high. But this was a new operation, and on a large scale. There were no proven standards to go by. Realizing this, Reserve's engineers provided ample and efficient access to machinery, allowing extra space for unanticipated situations. In three years of production this planning has paid off handsomely. Gravity Flow Saves Time and Money: This plant is on a rocky hillside, the car dumper about 270 ft above Lake Superior. In locating buildings and placing machinery the designers mad= good use of gravity flow, at considerable financial savings. In the concentrator building from rod mills to filters, gravity carries the material between all stages of the operation except one—the closed circuit pumping of concentrate between cone classifiers and ball mills. Since no machine is located directly above any other, an observer can stand on the truck ramp adjacent to the offices and laboratory and see practically every phase of activity in the huge building. The first mill section started in August 1955. After a day's run several modifications were made on auxiliary chutes and launders where spillage had occurred. This procedure was followed for the first

Jan 1, 1960

By A. H. Kline, E. B. Zimmer, Zay Jeffries

It is well known that many properties of a given metal vary with the size of grain or cell. For most industrial purposes, where high ultimate strength and high elastic limit are desired, the manufacturer tries to produce a fine-grained structure. For some purposes, for example in transformer iron, a coarse-grained structure is desirable. The terms fine-grained and coarse-grained are used only in a relative sense. For example, a fine-grained cast copper might have grains 100 times larger than coarse-grained high-speed steel. Similarly, a finegrained steel rail might have grains or cells 100 times larger than coarsegrained wire, which was made of steel from the same heat. In some metals, the change in grain size is more appreciable khan the changes in any of the properties determined by the tensile test. Furthermore, in metals which have been annealed or subjected to high temperatures, grain size may prove to be a better indication of the life of the metal in use than the tensile test. One of the authors was able to supplant the tensile test with grain-size determinations in the control of metal for a specific use, the latter determination being more indicative of the life of the metal part than the tensile test. A grain-size determination with a tensile stest is, of course, more valuable than either singly. At present there is a decided dearth of data on actual grain-size determinations in metals, and consequently a corresponding lack of ability to interpret the determinations after they are made. It would be desirable to have correlation made between grain size and properties of metals, comparing thousands of determinations. In this way, grain-size determinations might be interpreted in much the same manner that tensile tests are now. Several Methods of Measuring Grain Size One of the chief reasons why more grain-size measurements have not been made is the excessive work involved in making a determination.

Jan 1, 1916

By William K. Antle

The successful application of ther mo compression lead bonding to semicondtctor or thin-film electronic devices depends on the establishment of the associated parameters. The quality of a thermocompression bond is primarily related to the process temperature and bonding force. A technique using the coelyicient of friction is presented that both reduces the time necessary for determining optimum parameter values and increases the accuracy of the results. Modern theories of the friction process are used to develop mathernatical expressions for shear and tensile bond strengths in terms of friction measurements. A further application of the pararneter-deterlnination technique concerns the measurement of surface contamination that may affect thermocompression bonding. In spite of the extensive use of thermocompression bonding, adequate methods for determining the bonding parameters have not been utilized. The quality of the weld depends on the temperature, force, and time used. There is a definite value or range of values for each parameter which assures an optimum weld. The process now generally used to obtain these values is to make several weld samples at each parametric setting, determine the mean pull strength, and relate the maximum consistent strength to optimum weld conditions. This could involve a very large number of test samples if a thorough search of each parameter were made. Experience and prior knowledge can reduce this number somewhat by limiting the investigation to a range known to contain the correct value, but the time and effort involved are still objectionable. The problems associated with thermocompression bonding of interconnecting leads to semiconductor or thin-film devices can be alleviated by the application of a new technique for establishing the process parameters. Obtaining the correct temperature, force, and duration to assure an optimum bond is accomplished by a simple measurement of the coefficient of friction. This approach increases the accuracy of parameter determination and greatly reduces the time necessary to complete the process. The approach made can be better understood by analyzing the principles of adhesion and friction on which thermocompression bonding depends. When two flat polished surfaces are placed together, the area of actual contact is much less than the apparent area determined by the over-all dimensions of the surface. This is because the microscopic surface is covered with projections which prevent uniform contact. Careful measurements of the electrical resistance across the contacting surfaces indicate the actual area may only be 1100,000 of the apparent area.' Because the actual contact area is small, extremely high pressure results from moderate force. This will produce deformation and plastic flow at contact points of the microscopic projections. The process will terminate in the creation of a large number of minute welds formed at extreme pressure and cold-worked to strong, hard bonds. Load removal will generally result in fracture of most of these microbonds because of the residual elastic stresses, unless the materials are soft. Friction between metals is due to the formation and

Jan 1, 1967

By S. R. Zimmerley, S. F. Ravitz

High-grade cobalt concentrates were produced from the complex Blackbird ore with very good recovery in continuous pilot-plant operations in which a low-grade bulk cobaltite-pyrite flotation concentrate was roasted in a multiple-hearth furnace to oxidize the pyrite selectively. The cobaltite was floated from the resulting calcine.

Jan 1, 1950

For his achievement in building the Panama Canal, Major-Gen. George W. Goethals was presented, on May 22, the John Fritz medal, the highest mark of distinction in the engineering profession. In the absence, in Europe, of Clemens Herschel, chairman of the Board of Award, Charles F. Rand presided over the meeting. Col. John J. Carty, who was chairman of the Board of Award at the time the medal was awarded to Gen. Goethals, and who ordinarily would have presented the medal, was detained in Paris by Government work, so the presentation was made by Ambrose Swasey. When calling the assembly to order, the Chairman said: This medal has been awarded by a Board representing four of the National Engineering Societies: American Institute of Mining and Metallurgical Engineers, American Society of Civil Engineers, American Society of Mechanical Engineers, and American Institute of Electrical Engineers. The medal was established in 1902, in honor of that great American engineer, John Fritz, and has never been awarded except to very distinguished men. In. 1902, the first award was made to John Fritz for scientific and industrial achievement. In 1905, to Lord Kelvin for his work in cable telegraphy and other scientific attainments. In 1906, to George Westinghouse for the invention and development of the air brake. In 1907, to Alexander Graham Bell for the invention and introduction of the telephone. In 1908, to Thomas A. Edison for the invention of the duplex and quadruplex telegraph, the phonograph, the development of a commercially practical incandescent lamp, the development of a complete system of electric lighting, including dynamos, regulating devices, underground system protective devices and meters. In 1909, to Charles T. Porter for his work in advancing the knowledge of steam engineering and in improvements in engine construction. In 1910, to Alfred Noble for notable achievements as a civil engineer. In 1911, to Sir William H. White for notable achievements in naval architecture. In 1912, to Robert W. Hunt for his contributions to the early development of the Bessemer process. In 1914, to Professor John E. Sweet for his achievements in machine design. In 1915, to Dr. James Douglas for notable achievement in mining, metallurgy, education, and industrial welfare. In 1916, to Dr. Elihu Thomson for achievement in electrical invention, in electrical engineering and industrial development, and in scientific research. In. 1917, to Dr. Henry M. Howe for his investigations in metallurgy, especially in the metallography of iron and steel. In 1918, to J. Waldo Smith for achievement as engineer in providing the City of New York with a supply of water. And now to General Goethals for achievement as the builder of the Panama Canal_

Jan 7, 1919

By Victor Formanek, Paul Chataignon, Maurice Rey

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951

By Maurice Rey, Victor Formanek, Paul Chataignon

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951

By A. J. Lanza

The prevention of illness among the employees of the mining industry is especially important in view of the importance of the industry, the unsettled conditions of labor, which emphasize the economic necessity for conservation of labor, and for humanitarian reasons. The burden of chronic illness is altogether unwarranted and unnecessary. If the industry is to maintain its labor supply in an efficient manner and keep the standard high, it is essential that it make every effort to keep its labor in good physical condition. The basic principles underlying health conservation are the same for any industry, but they are here applied especially to the mining industry, and more particularly, perhaps, to metal mining, as it is with this phase of the industry that the writer is most familiar, and as it is conceded that metal mining presents more health hazards than coal mining. The first step in the prevention of illness lies in securing employees who are in sound health and free from organic disease. I do not mean that all men who go underground should be physically perfect, but they should be free from organic defects of the heart, lungs, and other organs, or from anatomical defects that would markedly increase their liability to accident. The number of men working underground in mines in this country whose physical condition totally unfits them for such work presents a situation that should not be allowed to continue, and which I believe is not equalled in any other industry in the country. There is but one way to secure men who come up to the required standard, and that is by a thorough physical examination before employment. I am fully aware of the objections felt toward such a procedure by many employers and employees. There is much to be said on both sides, but to any one who is at all familiar with the mining industry as it is today in this country, and who approaches the matter with an unbiased mind, there can be absolutely no doubt as to the necessity for physical examination. As a purely logical proposition this is self-evident, but there remains the further necessity of placing physical examinations on such a basis that they can be administered in a just and equitable manner free from the abuses and suspicions to which they have been subject in the past.

Jan 1, 1919

By John Shelton

ONE of the heaviest burdens uselessly cast by our mineral land laws upon the holder of the title conveyed by a patent from the United States is due to the provision excepting known veins from land patented as placer. In many instances the expense of defending such titles from the assaults of the owners of lode locations made upon the theory that the veins so located were known to exist at the date of the placer application for patent has exceeded many times the value of the land in question. Neither the lapse of time, however long after the issuance of the patent nor repeated adjudications by the courts serve to quiet such titles or to prevent them from being questioned. In the passage of laws providing for the acquisition of title to the mineral lands of the United States, Congress provided that the title to known veins should not pass from the United States by a patent based upon a placer location. As construed by the courts, the law (Sec. 2333 R.S.U.S.) provides that the applicant for a patent upon a placer claim may, if any vein of sufficient value to justify the expenditure of money in its development is known by him to exist within the boundaries thereof, include in his patent application an application for patent upon the vein as a lode claim; and failure to do so is to be deemed a conclusive declaration that the applicant makes no claim to the vein nor to an area of surface ground extending for 25 ft. (7.6 m.) on each side of its middle or center. As to such vein and, such area of enclosing surface ground under the circumstances stated, the title remains in, the United States notwithstanding the issuance of a patent that purports to convey the entire surface of a described area and everything beneath it, excepting only the segments of veins the apices of which lie outside of such area. Such known veins with such area of enclosing surface ground are, of course, at any time, so long as they remain unlocated, subject to location and appropriation in the same manner as other veins upon the public domain. The history of the operation of this law in one district will serve to illustrate its effect generally throughout the mining regions of the United States. In the Butte district, the mineral that first attracted the atten-

Jan 8, 1919

By Gerald C. Mathis

FERGUS County, Mont., shown in Fig. 1, is known for its once famous gold mines near the old towns of Gilt Edge, Maiden, and Kendall. But at Heath, a small farming community near the foothills of the Snowy Mountains, thousands of tons of gypsum have been mined since 1916. The value of the gold taken from the mines of Fergus County runs into millions of dollars; the value of the products made from the gypsum of the Heath mine is also in the millions. The gypsum mine will continue to produce for many years, while the gold mines are closed today. The Heath gypsum mine was developed by the Northwest Gypsum Co. in 1916. The products of the small mill built by this company were plaster, agricultural gypsum, and raw gypsum for cement manufacturing. The United States Gypsum Co. prospected the adjacent property in 1916 and 1917 by means of two adits and some exploration drill holes. During World War I, the company abandoned operations at Heath, but again became active in this area in 1928 hen it purchased all the property of the Northwest Gypsum Co. A long range program of expansion was begun with the building of a block plant and the purchase of additional land and mineral rights. A modern wall board plant was built in 1936. When the old wooden mill purchased from the Northwest Gypsum Co. burned in 1937, an all-metal calcining plant located at Blue Rapids, Kansas, was dismantled, moved to Heath, and erected on the site of the mill. In August 1951 a new mine was opened 3000 ft north of the mill. Rock is conveyed from the mine to the mill by an 18-in. belt conveyor. The Heath gypsum deposit lies at the base of the Ellis formation of Jurassic Age. The Ellis at Heath lies unconformably on the black fissle shale of the Heath formation of the Big Snowy Group, which is Mississippian in age. The strike of the gypsum bed is N45°E and the dip approximately 3" NW; the regional strike and dip of the area. The gypsum lies in a series of six layers separated from each other by thin seams of shale. The lower layer is composed of' gypsum and shale intermingled and is not of commercial grade. The upper five layers are high in purity, but only the middle four layers are mined on the advance, as the top layer is left for roof support. This top layer is mined on retreating operations at the same time the pillars are robbed. Total thickness of the gypsum layers varies from 12 to 14 ft. Fig. 2 shows the average thickness and arrangement of the layers. Mining Methods The mine was originally developed by driving an adit into the gypsum horizon. The Northwest Gypsum Co. mined in the top four layers, the top layer being split, leaving about 12 in. for roof support. A modified room and pillar method was used: entries were 15 ft wide and rooms varied between 20 and 30 ft and were turned on 90" from the entries. Crosscuts between the rooms left pillars from 10 to 20 ft square. The rock was loaded by hand into 1-ton mine cars and pulled to a central gathering point by mules; from the gathering point, mules or horses were used to pull the string of cars to the mill tipple. This method was continued by the United States Gypsum Co. from 1928 to 1937.

Jan 1, 1954

By F. W. Glaser

Metal-carbon-boron powder mixtures were hot pressed and the resulting specimens were studied by X-ray diffraction. It was found that regardless of the starting combination of the metal, carbon, or boron powders, a metal boride phase was always the major component in these samples. In the absence of carbon the boride phase formed on hot pressing depended only on the amount of boron present. Two new phases of the system Ti-B were found. They are Ti2B and Ti2B5. The existence of a controversial face-centered cubic phase of formula TiB was confirmed. Electrical resistivities were measured for various boride phases. It was found that the diborides are generally better conductors than the monoborides of the same metal. THE carbides and borides of the transition elements have very high melting points, in the range 2500° to 4000°C, and are therefore of interest as high temperature materials. The literature on the stability or chemical reactivity of these carbides and borides is very scarce. Various investigators'-" have demonstrated a relative instability of certain carbide phases in the presence of boron or boron-containing substances. In a recent publication, Glaserl demonstrated the stability of zirconium-boride (ZrB,) in the presence of carbon at temperatures in excess of approximately 2900°C, while during a preliminary investigation of boride phases, Steinitz' concluded that the diborides are stable in the presence of carbon while the monoborides of the fourth and fifth group are not, forming diborides plus carbides instead. Nelson, Willmore, and Womeldorph" have elaborated on the reaction B,C + 2TiC = 2TiB, + 3C, which was known to occur because of a relative instability of B,C and the great tendency towards TiB, formation at relatively low temperatures (approximately 1200°C). A similar study, involving as starting materials TiO, and B,C and resulting in TiB,, was recently described by Honak4, who observed the beginning of an exothermic reaction of a Ti0,-B,C powder mixture, which, when preheated in a hydrogen atmosphere to approximately 950°C, was carried to about 1600 °C by the heat of reaction. To shed more light on reactions of this type (Metal-C-B), the final product apparently always resulting in a boride phase at the expense of a carbide phase," a systematic investigation was started * Boride phases of various metals, as reported to date, are listed in Table I. and the following is an account of some of the results that were obtained. Materials, Preparation of Samples, Testing Methods The raw materials employed for this work consisted of various carbide, boride, and metal powders. as well as of boron and graphite powders. In cases where commercial grades of carbides were considered unsuitable because of low purity or excessive amounts of graphitic carbon, such carbide powders were prepared by this laboratory. The procedure for the preparation of carbide powders (zirconium carbide, titanium carbide, tantalum carbide, and niobium carbide) consisted of mixing graphite and the respective metal hydride powders in stoichio-metric proportions and subsequent heating of such mixtures in a hydrogen atmosphere in carbon crucibles. The heating was by high frequency to temperatures ranging between 1700" and 2100°C. The resulting carbide was then comminuted and screened to the desired particle size. ZrB, and TiB, powders were produced by the electrolysis of fused salt baths, according to the method described by Andriex.. The borides of niobium, vanadium, tantalum, molybdenum, chro-ium, and iron were obtained by mixing the respective metal and boron powders in the desired proportions. Such metal-boron mixtures were heated in a high frequency furnace to form boride powders. For each metal-carbon-boron group (Tables I1 through XI) a metal, its hydride, carbide or boride were mixed with carbon, boron or boron carbide powders. The additions of carbon, boron or boron carbide powders to any of these metals or metal compounds were calculated to satisfy a particular carbide or boride phase that according to the literature (Table I) had definitely been established by X-ray diffraction work. Samples of powder mixtures were hot pressed in graphite molds that were heated by direct conduction. The specimen dimensions were approximately 2.5X1X1 cm. Hot pressing temperatures were measured optically and maintained for approximately 30 sec under a constant pressure of about 1.3 ton per sq in. Wherever possible, an attempt to obtain maximum specimen density was made by temperature variation. Electrical resistivity testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp, at room temperature. To obtain electrical resistivities for specific carbide or boride phases, values were plotted as a function of the respective sample densities

Jan 1, 1953

By Louis V. Bender, R. E. H. Pomeroy, David H. Browne

E. P. Mathewson, Anaconda, Mont.—After hearing about the success of D. H. Browne with his furnaces, we in Anaconda decided we might venture into the field of pulverized coal for reverberatory smelting. We sent a delegation of investigators to see Mr. Browne and his work, and they returned, filled with enthusiasm, and said they would recommend it strongly.. We thereupon asked for an appropriation, and after some delay obtained the same and fitted up one furnace to use pulverized coal. We copied Mr. Browne's practice and his selection of machinery for drying and pulverizing coal; and we also copied the burner he used, which was a standard article on the market. We got an expert coal-dust machinery man to design our plant, and were very glad we did so as we avoided some of the unpleasantness that had been experienced at other plants through fires and minor explosions. I want to say, before describing our apparatus a little in detail, that we were quite familiar with the work of Mr. SÖrensen, the pioneer in the use of pulverized coal for copper smelting. Our attention had been called to it by Mr. Klepetko early in the game. And afterward we were familiar with the work done at Cananea by Mr. Shelby. We sent an expert to investigate the question 10 years ago. He examined the work of Mr. SÖrensen; and then went to the cement men and examined their work, and reported at great length that coal dust was the ideal fuel for them, as they took the ash from the coal and sold it as cement. He reported that coal-dust firing could not be made economical in reverberatory copper smelting, and his reasons were that a blanket of nonconducting material would cover the charge in a short time and insufficient heat would reach the charge proper, and we would have floaters over all our furnaces. The flues would be stopped by the dust that did not settle on the charge. We accepted that until our Irish friend got busy and showed us how to do it. Then we built a furnace which we thought was a slight improvement over Mr. Browne's. We put railroad tracks over our furnaces to draw the charge to the furnace. We had

Jan 1, 1915

By H. W. Hardings

Nearly every mining and metallurgical engineer will recall his early experience and method of producing step- or stage-reduction in preparing ore-samples for assay, in which he employecl idea, step- or stage-reduction simply because it was a self-evident fact that it would be easier to break coarse ore with a hammer than it would be to roll it back and forth under the muller, and alter having reduced it to a size easy for a rubbing or bucking division he then placed it under the muller on the bucking-board and further reduced it in proportion to the physical energy he wished to expend, which was generally the minimum to produce results. After this step in our experience me seem to have ceased to consider stage-reduction as mechanicallg essential, probably because it did not apply to individual exertion. Moreover, me did not retain the mass under the muller until it was all reduced to pass the 80-mesh assay-oftice screen, but practiced further step-reduction by screening out the fine in order that it should not interfere with subsequent work, replacing the coarse for further reduction on the bucking-board. It was many years after the bucking-board stage of metallurgical practice that we mere brought to a full realization that there was a more economical method in applying the crushing forces usually employed in metallurgical work by taking advantage of this individual experience and applying it to mechanical ends. We have made some advance to this end in bringing out the conical ball-and-pebble mill—a device which fairly well automatically adjusts power to the results obtained, mechanically repeating the bucking-board experience. In the action of the conical mill, theory is evolved from practice, rather than practice from theory, as is commonly the case.

Jan 1, 1914

By Andrew Hodge

ISSUES IN MINING LABOR The examination of mining labor issues is often confined to health, and safety. There are other issues, including the present state of mining manpower availability and utilization, and the nature of mineral industries' industrial relations, which are worthy of consideration. The state of the labor market for mining skills, the availability and utilization of mining engineers and related disciplines, the state of research and its employment of scientists and engineers, and the condition of mining industrial relations with all these groups, all have an important effect on the viability and economic health of the minerals production sector. PRODUCTION LABOR Why examine an industry's production labor market? People involved in an industry should be aware of what labor supplies will be relative to industry requirements. This advance information allows industry and government to plan ahead to alleviate problems by moving to affect labor supplies or to accommodate production to expected labor supplies. This is less costly and less painful than responding after the fact to labor market changes. Any industry requires some form of labor. Labor is especially important to the mining industry. Mining labor is well paid. Average annual earnings are higher than in manufacturing. Average hourly wages are also higher. Payroll costs form a high percentage of total cost in coal mining and nonmetallic minerals mining. In metal mining the percentage is comparable to the average for manufacturing. Payroll cost in oil and gas extraction is quite low, but a major proportion of cost is in the form of income to proprietors, i.e., unincorporated businesses. Mining labor is worthy of specific attention. The minerals extraction labor is unique in many ways. Mining labor and especially underground miners are differentiated from other "unskilled" labor. Miners cannot be considered as part of a larger labor pool. The mining labor market has exhibited a unique combination of characteristics. Mining is the only large sector of United States employment in which hourly wages are high and continuing to rise, yet employment declines. Although industry has introduced new labor-saving investments, and labor requirements continue to decline, there is evidence of a mining labor shortage. Specific problems have arisen in the mining labor market such as a present labor shortage in nonfuels mining. Understanding the causes and remedies for these specific problems is also important. These various problems and questions may be handled in a unified manner by examining the relationships of certain economic variables. The relationship that exists between changes in output, employment, labor productivity, and hours worked per week may be stated explicitly:

Jan 1, 1976

By T. Sterry Hunt

THIS remarkable mine, to which attention has lately been drawn, is situated not far from the New River, in Ashe County, North Carolina, on a spur of the Blue Ridge which lies between the main crest of this name and the so-called Iron Mountain, a part of the Unaka or Smoky Mountain range. It is on a true fissure-lode, which cuts the strata of gneiss and mica-schist of the region. These, which have the lithological characters of what I have called the Montalban or White Mountain series, have here a dip of about forty-five degrees to the southeast, while the lode is vertical, with a course north 60° east. Both the country-rock and the lode, as is usual in this region, are decomposed to considerable depths ; and the latter exhibits a cap of hydrous peroxide of iron or gossan, blocks of which, left by the denudation of the softer inclosing rock, are scattered over the surface, and first called attention to the locality as a source of iron ore. In sinking upon this lode, it was found that the porous gossan at a certain depth became charged with carbonate and red oxide of copper, and lower down was replaced by sulphuretted ores of this metal of remarkable richness. This deposit was worked for copper, in an irregular manner, before the late civil war, but was afterwards abandoned, and only reopened during the present year, by Messrs. S. S. & J. E. Clayton, of Baltimore. The outcrop has been traced for 1900 feet, and the sulphuretted copper ores have been met with in five shafts in a distance of 661 feet, a drift having moreover been carried for the above distance through the solid ore. The breadth of the lode, so far as opened, varies from six to eight feet to fourteen feet in places, and that of the outcrop of gossan is, in some parts, twenty feet. After comparing this deposit with the copper mines of Ducktown, Polk County, Tennessee, and those of Carroll County, Virginia, it is evident that we have, at Ore Knob, to do with the same kind of black ores as were met with in these mines, and will be noticed further on. Beneath the gossan, at Ore Knob, is found, in some parts, an iron-black, friable, drusy, crystalline, sulphuretted ore, inclosing grains of quartz, garnet, and magnetite, besides a black non-magnetic mineral, not attacked by nitric acid. This ore contains about 36 per cent. of copper, and portions have the mineralogical charac-

Jan 1, 1874

By T. Sterry Hunt

This remarkable mine, to which attention has lately been drawn, is situated not far from the New River, in Ashe County, North Carolina, on a spur of the Blue Ridge which lies between the main crest of this name and the so-called Iron Mountain, a part of the Unaka or Smoky Mountain range. It is on a true fissure-lode, which cuts the strata of gneiss and mica-schist of the region. These, which have the lithological characters of what I have called the Montalban or White Mountain series, have here a dip of about forty-five degrees to the southeast, while the lode is vertical, with a course north 60' east. Both the country-rock and the lode, as is usual in this region, are decomposed to considerable depths; and the latter exhibits a cap of hydrous peroxide of iron or gossan, blocks of which, left by the denudation of the softer inclosing rock, are scattered over the surface, and first called attention to the locality as a source of iron ore. In sinking upon this lode, it was found that the porous gossan at a certain depth became charged with carbonate and red oxide of copper, and lower down was replaced by sulphuretted ores of this metal of remarkable richness. This deposit was worked for copper, in an irregular manner, before the late civil war, but was afterwards abandoned, and only reopened during the present year, by Messrs. S. S. & J. E. Clayton, of Baltimore. The outcrop has been traced for 1900 feet, and the sulphuretted copper ores have been met with in five shafts in a distance of 661 feet, a drift having moreover been carried for the above distance through the solid ore. The breadth of the lode, so far as opened, varies from six to eight feet to fourteen feet in places, and that of the outcrop of gossan is, in some parts, twenty feet. After comparing this deposit with the copper mines of Ducktown, Polk County, Tennessee, and those of Carroll County, Virginia, it is evident that we have, at Ore Knob, to do with the same kind of black ores as were met with in these mines, and will be noticed further on, Beneath the gossan, at Ore Knob, is found, in some parts, an iron-black, friable, drusy, crystalline, sulphuretted ore, inclosing grains of quartz, garnet, and magnetite, besides a black non-magnetic mineral, not attacked by nitric acid. This ore contains about 36 per cent. of copper, and portions have the mineralogical charac-