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By H. E. T. Haultain

The study of rock crushing or grinding in tube-mills is difficult on account of the large size of the units employed in the field and the large number of variables entering into the problem. Three or four years ago, in the laboratory of the Department of Mining Engineering of the University of Toronto, a serious effort was commenced to study the matter under laboratory conditions. Experiments were carried on in a cylindrical tube-mill 18 in. long and 12 in. in diameter, inside measurements,

Jan 1, 1923

By H. E. T. Haultain

The study of rock crushing or grinding in tube-mills is difficult on account of the large size of the units employed in the field and the large number of variables entering into the problem. Three or four years ago, in the laboratory of the Department of Mining Engineering of the University of Toronto, a serious effort was commenced to study the matter under laboratory conditions. Experiments were carried on in a cylindrical tube-mill 18 in. long and 12 in. in diameter, inside measurements,

Jan 1, 1923

By K. C. Strebig, C. W. Schultz, A. A. Selim

For some time researchers have attempted to in- crease drilling efficiency (and therefore reduce costs) by adding certain chemical agents to the circulating medium. The effect of some organic additives on the diamond drilling of quartzite was recently investigated in the laboratory by personnel of the U. S. Bureau of Mines. In these tests, the penetration rate and bit life were found to increase with the use of additives. In addition, an economic analysis of a hypothetical 1000-ft hole showed that additives can reduce drilling costs by 30%. Wetting Agents Improve Drilling Efficiency Much of the interest in the use of wetting agents to improve drilling efficiency is the result of an observation made by Rehbinder, Shreiner, and Zhigach.1 These investigators postulated that drilling creates a region of increased crack formation directly below the bit and that a circulating medium that wets the rock will also penetrate the micro- cracks of the predestruction zone. Increasing the molecular affiinity (wetting ability) of these circulating media for the surface of the rock helps the deformation and destruction by softening the rock in the zone of increased crack formation. In this manner, the hardness or strength of the rock is decreased as the medium wets the rock in the predestruction zone. This is known as the "Rehbinder effect." Rehbinder's work has prompted many investigators to examine the relationship between the use of additives and the mechanical destruction of rock. Engelmann, Terichow and Selim reported that the maximum penetration of the rock by a diamond point in a solution environment was at the isoelectric point of the mineral and solution interface.2 Improvement in rock breakage with the use of additives was observed by Frangiskos and Smith.3 Joris and McLaren suggest that additives having a lower surface tension than water will also be more efficient in cooling the diamonds.4 Additives help remove fine cuttings from the face of the bit and improve efficiency. The latter two authors also report an improvement in impregnated bit life and penetration rates with the use of soluble oil additives. All of these investigations were initiated in the hope of discovering what economic benefits will accrue with the use of additives.

Jan 10, 1969

By Walter M. Stephen

MODERN developments in alloy steels have been so rapid and diverse that engineering practice has scarcely had time to re-appraise all items of past experience wherein conclusions became axiomatic under conditions that no longer apply. A case in point is the wet screening of abrasive ores within the fine range still looked upon as belonging exclusively to classifiers. By virtue of the development of stainless steels (18 per cent Cr, 8 per cent Ni), it is no longer true that classifiers are more economical than screens in closed circuit with large-tonnage ball or rod mills at 65 or even 100 mesh, provided a selective overgrind of the higher-gravity constituents of the ore is not desired. Wet screening of ores is a highly corrosive as well as an abrasive operation, because of the inevitably high degree of oxygenation of the water. Screen cloth of ordinary or spring-steel wire almost at once becomes pitted arid covered with a film of corrosion products, which causes rust-blinding of fine-mesh screens and offers high frictional impedance to the flow of ore particles. On the other hand, the well-known properties of stainless steel enable it to maintain a bright surface, and so to eliminate blinding either by ore particles or by corrosion products. That a large-tonnage mill grinding hard ore to 65 mesh can be operated economically in closed circuit with screens instead of classifiers has recently been demonstrated at the Copper Cliff concentrator of the International Nickel Co.; in the test to be described, a 6 ½ by 12 ½ -ft. Marcy rod mill ground from 625 to 820 tons of ore per day to approximately 65 mesh, operating in closed circuit with three 4 by 5-ft. Hum-mer screens, without any classifier. Stainless-steel cloth gave an indicated life of several months. There was no difficulty with blinding, yet dilution and spray water could be controlled so that screen undersize averaged not less than 40 per cent solids. In contrast, ordinary carbon steel was pitted and blind with rust within 40 hours.

Jan 1, 1938

By T. Reed Woodbridge

The object of this paper is to bring to notice a method in use at the Cedar Point laboratory of Witherbees, Sherman & Co., for determining the phosphorus in the ore mined at Mineville, N. Y. This ore is magnetite, with a gangue containing crystals of apatite. In 1886, Mr. H. F. Dawes, then head chemist at the works, suggested that as all the phosphorus seemed to be in the apatite, it could be obtained in solution by dilute nitric acid. After some experimenting the following method was adopted, and has proved invaluable for rapidity and ease; half a dozen determinations requiring very little more time or trouble than one. From + to 10 grammes of ore are weighed into a 150 c.c. beaker; 50 C.C. hot water and 10 c.c. strong nitric acid are added; the beaker is covered and the contents are boiled for 1/2 hour (10 minutes sometimes proves sufficient; but 4 hour is safer). The bumping which ensues if more than & gramme is used need cause no trouble. The hot solution is filtered into a 250 C.C. beaker. The filtration and washing (with hot water) proceed rapidly, as the magnetite itself is but slightly acted upon. After the addition of 15 C.C. ammonia and 15 c.c. nitric acid, the solution is cooled to 45' C., and from 15 to 40 C.C. of molybdic acid solution is added and stirred vigorously. In 5 minutes the precipitate will be down, and the determination can be finished by any good method. At Cedar Point the method more commonly used is weighing as yellow salt. Good washed filter-paper is used, No. 0 Swedish being preferred; and dozen 3 1/2-inch filters are numbered and dried and weighed at 110°C. These are always kept in stock. The yellow salt is filtered on one of these, washed with dilute nitric acid (2 per cent. by volume); dried for 1 hour at 110' C., and then weighed, 1.63 per cent. of weight being calculated as phosphorus. The filters vary in the two weighings from

Jan 1, 1889

By R. L. Fleischer, R. S. Davis

BICRYSTAL specimens grown from the melt have been used extensively for investigations of the influence of grain boundaries on plastic deformation. The bicrystals are usually of predetermined orientation prepared by seeded growth from the melt in milled graphite boats. This technique has been described in detail by Chalmers.' Since the direction that the grain boundary follows during growth is affected by both thermal conditions and crystallography, a difficulty arises in maintaining the grain boundary position constant along the length of the specimen. This problem is particularly

Jan 1, 1960

By Rudolph G. Wuerker

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

Jan 1, 1961

By Y. Nakada, E. J. Fasiska, A. S. Keh, L. Zwell

DURING an investigation of solid-solution hardening of nickel by carbon,' we found that there were no reliable data on the dilating effect of dissolved carbon on the unit cell of nickel. Bernier2 reported an increase in lattice parameter of nickel (3.523A) when an unknown amount of carbon was introduced into solid solution (3.536A). Similarly KG, Tsien, and Misek3 found an increase from 3.523 to 3.531A when nickel was carburized. strong4 studied the variation of nickel lattice constant as a function of dissolved carbon. However, in his case carbon was introduced into nickel by solidifying the melt at 65 kbar. Therefore, his carbon concentrations were much above the highest equilibrium solubility limit5 (2.7 at. pct C at 1 atm). Knowledge of the lattice mismatch between solute and solvent is essential in understanding the mechanism of solid-solution hardening. Therefore, we decided to determine the dilation of the nickel lattice by carbon under the more usual conditions of atmospheric pressure. The material used was Inco Electrolytic Nickel of 99.95 pct purity, as specified by the supplier. The impurity contents in wt pct were: Fe, 0.01; Cu, 0.01; Co, 0.03; 0, 0.005; C, Si, S, N, trace. To this base material various amounts of AUC-grade high-purity carbon were added during vacuum induction casting. Ingots, 2 in. in diam, were heated in a muffle furnace at 1000°C for i hr., hot-rolled to 1/2-in. thickness, and quenched into brine. All ingots with carbon concentration greater than 0.98 at. pct were enclosed in a cast iron box during the heating to minimize decar-burization. Small pieces were then either swaged down to 0.028-in.-diam wire or cold-rolled to 0.010-in.-thick sheets. After the final cold reduction in area of 50 pct, the specimens were recrystallized by heating in evacuated capsules at 1100°C for 60 to 80 sec and then quenched into brine. The final grain size was 50 to 100 µ. The carbon contents of the alloys, Table I, were determined by a combustion method

Jan 1, 1969

By P. Barnes

It may he of interest, and perhaps of inzportance, to the members of the Institute that specific mention should be made in detail of the great value of this method of copying or photographing all kinds of tracings." Several samples are laid upon the table which may serve as illustrations of the results obtained. Some of these show slight imperfections, depending upon the character of the tracing, and upon the length of the exposure to the light, but it may be clearly seen that even a faint copy would be quite available for actual use. The process is believed to be of French origin, and has been used for many years. Special attention seems to have been directed to it recently, and its great value to engineers appears likely to be fully recognized. The manipulations required are of the simplest possible kind, and are entirely within the skill and comprehension of any office boy who can be trusted to copy a letter in an ordinary press. These particulars may be summarized somewhat thus: 1. Provide a flat board as large as the tracing which is to be copied. 2. Lay on this hoard two or three thicknesses of common blanket, or its equivalent, to give a slightly yielding backing for the paper. 3. Lay on the blanket the prepared paper with the sensitive side uppermost. 4. Lay on this paper the tracing, smoothing it out as perfectly as possible so as to insure a perfect contact with the paper. 5. Lay on the tracing a plate of clear glass, which should be heavy enough to press the tracing close down upon the paper. Ordinary plate-glass of 3/8" thickness is quite sufficient. 6. Expose the whole to a clear sunlight, by pushing it out on a shelf from an ordinary window, or in any other convenient way, for six to ten minutes. If a clear skylight only can be had, the exposure must be continued for thirty or forty-five minutes, and under a cloudy sky, sixty to ninety minutes may be needed.

Jan 1, 1879

By Frank C. Greene

Missouri has had one of the best years in history in the development of gas, the 49 completed gas wells having an average of nearly 1,000,000 cu. ft. initial open flow. Altogether 101 wells were drilled in the western part of the state, from Andrew County on the north to Vernon County on the south. Of these 49 were gas wells (including four old wells drilled deeper) with an initial open flow of 48,850,295 cu. ft., eight were oil wells (including one old well drilled deeper) with an initial capacity of 125 bbl. per day and 44 were dry holes (including five old wells drilled deeper). All the oil wells were in previously discovered pools in Jackson and Cass Counties. The outstanding discovery was a "shoestring" of a sand that is termed the Bartlesville, trending northwest and southeast across townships 48 and 49 N., R. 32 W., in central Jackson County. The sand is believed to be a narrow channel or bar, probably not over 800 ft. wide, lying at a higher horizon than the Bluejacket or true Bartlesville sand. A total of 32 wells with 47,453,080 cu. ft. initial open flow has been completed along the 6 miles of the shoestring. The largest individual well had an open flow of 4,500,000 cu. ft. The depth of these wells ranges from 350 to 635 ft., depending on surface elevation. The rock pressure ranges from 145 to 169 pounds. The Missouri Valley Gas and Oil Co. and Panhandle Eastern Pipe Line Co. have laid pipe lines into the area and most of the wells are now connected. In other parts of Jackson County and in other counties of the state there was very little activity during 1937. Of the 101 completions, 88 were in Jackson County. Cass County had five oil wells and three dry holes, Bates County one dry hole and Vernon County two dry holes. In the northern counties, Andrew and Clinton were represented by one dry hole each. At the end of 1937 drilling and leasing operations were very active and wildcatting promises to feature the coming year.

Jan 1, 1938

By Walter Stephen

MODERN developments in alloy steels have been so rapid and diverse that engineering practice has scarcely had time to re-appraise all items of past experience wherein conclusions became axiomatic under conditions that no longer apply. A case in point is the wet screening of abrasive ores within the fine range still looked upon as belonging exclusively to classifiers. By virtue of the development of stainless steels (18 per cent Cr, 8 per cent Ni), it is no longer true that classifiers are more economical than screens in closed circuit with large-tonnage ball or rod mills at 65 or even 100 mesh, provided a selective overgrind of the higher-gravity constitu-ents of the ore is not desired. Wet screening of ores is a highly corrosive as well as an abrasive opera-tion, because of the inevitably high degree of oxygenation of the water. Screen cloth of ordinary or spring-steel wire almost at once becomes pitted and covered with a film of corrosion products, which causes rust-blinding of fine-mesh screens and offers high frictional impedance to the flow of ore particles. On the other hand, the well-known properties of stainless steel enable it to maintain a bright surface, and so to eliminate blinding either by ore particles or by corrosion products. That a large-tonnage mill grinding hard ore to 65 mesh can be oper-ated economically in closed circuit with screens instead of classifiers has recently been demonstrated at the Copper Cliff concentrator of the International Nickel Co.; in the test to be described, a 6 ½ by 12 ½ -ft. Marcy rod mill ground from 625 to 820 tons. of ore per day to approxi-mately 65 mesh, operating in closed circuit with three 4 by 5-ft. Hum-mer screens, without any classifier.. Stainless-steel cloth gave an indicated life of several months. There was no difficulty with blinding, yet dilution and spray water could be controlled so that screen undersize averaged not less than 40 per cent solids. In contrast, ordinary carbon steel was pitted and blind with rust within 40 hours.

Jan 1, 1938

By Best W. N.

Discussion of the paper of W. N. BEST, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1527 to 1537. WILLIAM A. WILLIAMS, San Francisco, Cal.-I would like to ask whether .Mr. Best ever had any experience with an oil burner that used neither air nor steam? W. N. BEST, New York, N. Y.-Yes. This type is commonly known as the "mechanical spray burner" and uses oil heated under high pressure to above its vaporizing point. These burners are not as efficient as the atomizing type for the following reasons: 1. They produce a round flame which; as with any other type of burner, must pass over a flat surface. A round flame cannot fit a flat surface. 2. They do not evenly distribute the heat, resulting in localized heat. 3. The outlet through which the fuel passes is very small; so all gravities of oil, especially oil containing sand, cannot be burned. 4. Their construction is such that they must be cleaned frequently, as the residuum in the fuel clogs the burner. 5. The oil opening being small, the capacity of each burner is small, so that many burners must be used in a boiler or furnace. (The fewer burners there are, the more accurately they can be regulated.) In marine boilers, these burners are largely used, because they do not require either steam or air for atomization. However, there are other methods by which this objection to other types can be eliminated, such as by the use of a rotary blower and steam turbine engine, the exhaust front the engine passing into the engine condenser, thus obviating loss of water. Mechanical burners are rarely used in shops. I know of but one power plant using them. With mechanical burners, the fuel must be maintained at a high pressure. On board naval vessels, some mechanical burners demand an oil pressure of from 100 to 6001b. It is advisable to reduce the pressure as much as possible, as fractured pipes or fittings are particularly dangerous, for the heated oil escapes as a vapor. In such cases there is liability of an explosion caused by spontaneous combustion.

Jan 12, 1915

By Stephen R. Holsinger

During 1972, Asarco's Silver Bell Unit embarked upon a project to test a digital computer-controlled grinding circuit against the performance of its other five grinding lines. The planning, implementation, and subsequent outcome of that project has been previously reported in a paper by Pittsl, et al. This paper will describe the solutions to major problems incurred during the implementation of this control strategy on the remaining five primary grinding lines. Changes made in operating philosophy and methods during the expansion will also be discussed.

Jan 1, 1979

By George V. Smith, Daniel E. Sonon

Various mechanical properties of the Ni-Co-C alloy system were investigated to delineate the strengthening effect of carbon. Carbon concentration, cobalt concentration, vain size, temperature, and strain rate were varied so that thermal activation analysis and the Hall-Petch analysis could be used to evaluate the strengthening effect of carbon. Increasing carbon increased the strength of nickel and a Ni-60 pct Co alloy , with the effect becoming more pronounced at lower temperatures. Yield stress depended linearly on carbon concentration in nickel, but it depended on the square root of carbon concentration in the Ni-60 pct Co alloy. The Hall-Petch slope of nickel increased with carbon concentration; however, that of the Ni-60 pct Co alloy did not. The yielding behavior of these alloys was sensitive to composition, grain size, and temperature. Cobalt eliminated serrations in the flow curve of carbon-containing nickel at 300' and weakened them severely at higher temperatures. Pairs, or clusters, of carbon atoms appear to be responsible for the observed strengthening behavior. FLINN' conducted several experiments with carbon in nickel in an effort to provide information on the strengthening effect of interstitial impurities in solid solution in fcc metals and alloys. Strengthening which increased with decreasing temperature led him to conclude that carbon causes Cottrell locking in nickel. Fleischer2 analyzed Flinn's data and calculated that the strengthening effect of carbon in nickel was smaller by a factor of fifty than the strengthening effect of carbon in a! iron. Fleischer2 termed the magnitude of strengthening of carbon in nickel "gradual" and that of carbon in a! iron "rapid". He attributed "gradual" hardening to hydrostatic strains and localized changes in modulus of elasticity around solute atoms, whereas he attributed "rapid" hardening to tetragonal strains around solute atoms. Sukhovarov et a1.3-7 reported strain aging and serrated plastic flow in nickel, both of which they attributed to the presence of carbon. Serrated plastic flow has been rationalized by a process involving a series of dislocation pinning and multiplication steps.8, This process is more probable when screw dislocations are strongly pinned. Screw dislocations cannot be pinned by pure hydrostatic forces from the symmetrical strains of an interstitial impurity in an fcc lattice, except for small, second-order effects. However, they might be pinned by localized changes in modulus of elasticity around solute atoms,' by the pinning of the edge components of the partial dislocations of an extended screw dislo~ation,'~ or by clustered groups of solute atoms whose net elastic stress field is unsymmetric. The purpose of the present work was to investigate various mechanical properties of the Ni-Co-C a1loy system which are sensitive to pinning effects in order to delineate the specific pinning mechanism of carbon. Carbon concentration, grain size, temperature, and strain rate were varied so that thermal-activation analysis and the Hall-Petch analysis could be used to evaluate the pinning mechanism. Cobalt was added to lower stacking fault energy so that the number and extension of split, screw dislocations would be increased in order to test the possibility of pinning by carbon at extended screw dislocations. EXPERIMENTAL PROCEDURE Nickel and cobalt (both 99.98 pct-. pure) were melted with graphite in stabilized zirconia crucibles and cast at lo-' Torr to form Ni-C and Ni-60 pctCo-C alloys. Two ingots were heated to 1250°C and were forged to 1-in.-sq bars. These bars were machined to 4-in.-round bars, and then swaged cold to 0.144-in. -diam rods. Reductions in area of approximately 75pct were used with intermediate anneals at 900°C for 1 hr. The carbon content of batches of 0.144-in.-diam rods from each ingot was reduced to two levels by annealing 5-in. lengths in palladium-purified, dry hydrogen at 1100°C for 25 and 100 hr. The remaining material from each ingot was annealed at 10"5 Torr for 1 hr at 1100"~. These treatments gave a total of three carbon levels for both the nickel and the Ni-60 pct Co alloy. The 0.144-in.-diam rods were swaged to 70-mil wire, cut into test specimens, and then re crystallized at lom5 Torr in capsules for 1 hr at temperatures ranging from 760" to 1050" ~. The capsules were broken and the specimens were immediately quenched into water. Average grain size was measured using Hilliard's method of circular intercepts." Annealing twin boundary intercepts were counted in addition to grain boundary intercepts to establish an average grain size. Average grain sizes ranged from 5 to 140 p depending on the cobalt concentration and re-crystallization temperature. Tension tests were made in duplicate at various temperatures at a crosshead speed of 8.34 x 10"4 in. per sec with an Instron Universal Testing Machine. Specimens of 1-in. gage length with soldered ball ends were used at atmospheric and cryogenic temperatures. Pinch grips were used on specimens at elevated tem-

Jan 1, 1969

By George Haworth

ELECTRICAL illumination of shafts, stations, and haulageways has been successfully practiced for many years, but its use in drifts and stopes where mining operations are carried on has- been limited. The large underground drifts of the Tri-State field present a lighting problem that is not satisfactorily solved by the use of the carbide lamp. It has, for some time, been the policy of the Anna Beaver mine to provide ample lighting throughout the underground haulage drifts and working faces. This has, in the

Jan 6, 1928

By Massimo Guarascio

Computer data processing and ore reserve evaluation techniques, mainly based on geostatistical methodologies, have been developed at Agip Mining Division with the assistance of the Department of Mining Engineering of the University of Rome. A number of computer programs are available when facing problems such as optimization of sampling patterns, minable reserve estimation, grade control of output, and so on. In the present paper, the aims and the criteria followed in developing these programs are discussed. Some recent examples of application are also cited.

Jan 1, 1977

Jan 1, 1965

By S. C. Dhara

A process of solvent extraction and separation of platinum group metals (PGM) and gold using primary, secondary, tertiary, and quarternary organic amines has been briefly described. The effects of amine structures; the use of diluents; the principle of synergism and antisynergism in the mixed extractants; the oxidation states of metal ions are explained in the amine extraction process of precious metals.

Jan 1, 1984

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950