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By H. Kahata, I. Iwasaki, Y. Takahasi

A combined process of segregation roasting-flota-tion or magnetic separation was developed to recover nickel from lateritic iron ores and oxidized nickel ores. An ore was mixed with a halide, such as sodium or calcium chloride, and a solid reductant, and roasted, whereby the nickel content was segregated out as discrete metallic particles. Either by magnetic separation, or by flotation using a sulfhydryl collector together with a heavy metal salt as an activator, the metallic nickel could be concentrated, Effects of such variables as the types and amounts of the halide and solid reductant addition and of the roasting conditions were extensively investigated. The concentration results on several types of ores from Japan, the Philippines, and New Caledonia are presented. Laterite is a residual product of rock decay in tropical and subtropical regions, and consists mainly of hydrated oxides of iron and alumina. Those derived from serpentine sometimes become enriched in nickel, cobalt, and chromium contents. Oxidized nickel ores are of the similar origin, but their nickel as well as silica contents are higher due to gamierite-type silicates. Apparently, nickel enrichment is more pronounced in the transition region between the surface layer of iron laterite and the underlying serpentine. Iron laterites often contain over 50% iron, and their reserve is reported to exceed 22 billion tons, corresponding approximately to 20% of the world iron ore reserve.1 It is readily apparent, therefore, why the iron laterites have attracted much attention of the steel industry as a potential source of iron ores. Numerous attempts to remove nickel and chromium as byproducts, have been reported in literature.' Worldwide discoveries of high-grade iron ore deposits in recent years have inevitably lessened the interests in iron laterites. However, in view of the tremendous potential for their gross value and supplies of nickel, cobalt, chromium, and alumina along with iron, the problem remains as a challenge. Much of the chromium in laterites is present in the form of relatively coarse particles of chromite, and various classification methods have successfully been applied for its removal.2,3 The nickel, however, is intimately associated with limonite, and ordinary concentration techniques are totally ineffective. Much attention has, therefore, been given to hydro-metallurgical or pyrometallurgical means. Yet, all the known processes appear to have limitations either economically or for the use of products as iron raw materials due to a high residual content of nickel. Some attempts have been made to pre-roast laterites or oxidized nickel ores, particularly with sulfidizing agents, and to remove nickel either by magnetic separation,' or by flotation.4 It is apparent that any such concentration process would require grain growth of nickel during roasting for effective separation. Oxidized copper ores are reported to be concentrated by the segregation roasting-flotation process,5 in which the ores are roasted with a chloridizing agent and a carbonaceous reductant in order to promote the growth of metallic copper through repeated cycles of copper chloride volatilization and its reduction on the solid reductant surfaces. Examination of a vapor pressure-temperature diagram of various metal chlorides indicates that a separation of nickel from iron may be effected by a similar process. In fact, the segregation roasting of laterites was reported to increase the extraction of nickel by the ammonia leach process, as compared to the ordinary reduction roasting.6 In the present article some of the preliminary experimental results of the segregation roasting, followed by either flotation or magnetic separation, on laterites and oxidized nickel ores are reported. The effects of various parameters in the roasting as well as in the concentration steps are discussed. MATERIALS AND METHODS An oxidized nickel ore from Thio, New Caledonia, and three laterites from Homonhon, the Philippines, Wakasa and Miyagawa, Japan, were selected for the

Jan 1, 1967

By T. Rosenqvist

From the chemical, metallurgical, and mineralogical points of view, the importance of thermodynamic data for metal-sulphides and sulphur dissolved in molten metal has long been realized. Such data will give a basis for thermo-dynamic calculations of processes such as roasting and the distribution of sulphur between molten metal and slags. Furthermore, it will help us understand the chemical forces which tie sulphur to the metal and to the melt. Thermodynamic studies of solid sulphides and the equilibria between solid sulphides and metals have been carried out in a rather large number of cases by several investigators. An excellent review of this work is given by Kelley.1 On the other hand, very little is known about the thermodynamic properties of molten sulphides and of sulphur dissolved in molten metal. The only system which previously has been investigated in this respect is the iron/sulphur system. The purpose of the present investigation was primarily to obtain further data for metalisulphur melts and the system silver/sulphur was chosen, not because this system was expected to be of special interest in itself, but because the silver/sulphur system is a typical example of a metal/sulphur system. Because of the low melting temperatures, the work could be carried out without appreciable furnace and refractory difficulties. The sulphur in this system possesses a rather high escaping tendency compared to most other metal/sulphur systems. By the method employed (reaction with hydrogen to form hydrogen sulphide) this gives ratios Ph2s/Ph2 up to 0.30, which may be determined accurately. 'rhermodynamic investigations of the heterogeneous reaction Ag2S +H2 —+ 2Ag + H2S have previously been carried out by Pelabon,2 Keyes and Felsing,3 Jellineb and Zakowski,4 Wat-anabe,6 and Britzke and Kapustinsky.6 Their results are in rather poor agreement. Experimental Part PRINCIPLE In the present invehgation the escaping tendency of sulphur from the condensed phase was determined by the reaction: S + H2 = H2S The ratio Ph2s/Ph2 is at constant temperature, directly proportional to the escaping tendency of sulphur and to its chemical activity in the condensed phase. (This ratio will subsequently be denoted by H2S/H2.) From this ratio and its variation with temperature and with change in the com- position of the condensed phase, thermodyrlamic quantities such as free energy and heat of reaction can be derived. The apparatus used is shown in Fig 1. The silver/sulphur alloy was placed in a crucible inside a refractory tube and mounted inside the furnace to the left. The tube was a part of a closed, gas-tight system in which the gas mixture could circulate until equilibrium was established. Circulation was maintained by the glass propeller to the right, driven by an external magnet, and promoted by the chimney action of the furnace. The gas passed up through the furnace, down into the crucible where it came in contact with the alloy, passed rapidly up through a narrow tube and out of the hot zone. After equilibrium was established between the gas and the condensed phase, the composition of the gas mixture was determined from its density. In its circulation, the gas mixture passed through a chamber (lower right on Fig 1) containing a buoyancy-balance, where the density of the gas was determined by magnetic balancing. From the measured density,

Jan 1, 1950

AT A MEETING of the Shareholders of the Russo-Asiatic Cons. Ltd., in London, Oct. 23, 1922, LESLIE URQUHART, chairman of the com- pany made the following statement:* I come now to our recent negotiations with the Soviet Government and to the agreement which has resulted from them. You will remember that the conference at The Hague broke up without having achieved anything very definite. It was not, however, a failure. It elicited from M. Litvinoff an offer which will, I think, come to be regarded as a milestone in the progress of Russia from a ruinous and unpracticable Communism towards a modified form of capitalism. The offer made by M. Litvinoff at The Hague amounted in effect to this: that in return for political recognition on our part the Soviet Government would first acknowl-edge its liability for Russia's national foreign debts, and, secondly, would give the original foreign owners of property in Russia effective compensation. A very great advance that. It showed-and there have been many other signs to confirm it-how real and persistent has been the internal evolution of Russia during the past year from Marxism to the economics of the Western world. I will not now detain you with the reasons why M. Litvinoff's highly promising and significant offer came to nothing. The fact that it had been made and the further fact that The Hague Conference had separated indefinitely were the important things. The first fact seemed to indicate that the Soviet rulers, after all, proved to be people with whom one could do business. The second fact rather emphatically showed that the way to do business with them was not by unwieldy poly-glot conferences of ministers, officials and experts representing a few dozen different governments and a few dozen different sets of national interests. That method had been tried at Genoa. It was tried again at The Hague. Each time it failed, and having failed it left the road clear for a simpler and more direct approach.

Jan 12, 1922

By E. C. Burke

IN view of rather widespread use of calcium as an alloying addition to magnesium alloys, it is rather surprising to find that, although the general features of the Mg-Ca equilibrium diagram are known with a fair degree of certainty,' ," considerable ambiguity concerning the solid solubility of calcium in magnesium exists. By using the disappearing phase technique in a metallographic study, Haughton' found that 0.6 pct Ca was soluble at 300°C and 1.8 pct was soluble at 516°C, the eutectic temperature

Jan 1, 1956

By Edward Steidle

THAT veterans are crowding the colleges is no longer news; 78 per cent of the 1916-47 enrollment in mineral industries curricula in the United States were veterans, but the rapid comeback from an estimated 1262 total mineral industries students in 1944-45 to 11,422 in 1946-47 is almost astonishing. The figure, which includes 1008 graduate students, is a substantial increase over the previous top record of 9619 in 1938-39. A small part of the increase is caused by the larger number of women entering the field, of whom there were c 9 in 1916-47. Petroleum leads the curricula with 34.5 % of the enrollment, metallurgy is second with 28%, and mining is third with 18%. Table 1. shows all curricula offered and those accredited by ECPD. Using the Mississippi River as a dividing line, 31 colleges in the East and 27 in the West offer curricula in the mineral industries.

Jan 1, 1948

By Earl Ingerson

BORE surfaces of used guns commonly show a pattern of cracks in various degrees of development. It has been suggested that these cracks may aid erosion by providing channelways for the gases, eventually leading to the tearing out of blocks of metal. Under the general studies of gun erosion conducted at the Geophysical Laboratory it appeared desirable to consider this factor, and to determine the resistance to surface cracking offered by gun steel and by various other materials that might be used in the bores of guns. METHOD AND APPARATUS In order to make such a determination it is necessary to have (I) an arrangement in which the surface to be studied can be subjected to conditions similar to those in a gun with respect to temperature, pressure (developed by explosion gases), composition of the gases and length of time the surface is exposed to the gases; and (2) a specimen that can be examined readily after any number of shots, and then fired again, if necessary. The first of these conditions can be met by using an explosion vessel designed by H. S. Roberts of the Geophysical Laboratory. Fig I shows a cross section of the apparatus. The "gun" G from which the charge is fired is made from the receiver of a caliber 0.30 army rifle, M1903, and the charges are prepared in caliber 0.30 cartridge cases. The test specimen S is held in place by a cone-shaped plug P and by a steel ,bridge B which is bolted to the outside of the explosion vessel on either side of the section shown. The plug, in turn, is held in place by a screw collar C. Maximum pressure is controlled by a brass rupture disk R. Part of the explosion gases flow past the two flat areas on S. st the two flat areas on S. Temperature and composition of gases, and the time before the rupture disk breaks, can be controlled by amount and kind of powder used, and pressure can be controlled by using rupture disks of different thickness. While the explosion vessel used was not designed so that temperature and pressure could be measured, in other vessels of closely similar size and shape containing proportionate charges of the same kind of powder as that used for standard testing procedure, values of 2700°K and 5000 psi were obtained. Since the orifices past the flat areas on the plug are small compared to the rupture disk hole (1:16), most of the gas goes out through the rupture disk when it breaks. The amount that goes by the plug depends on (I) the pressure attained before the rupture disk breaks and (2) the time it takes for this pressure to be built UP. The second condition (examination at will after any firing) is met by using for specimens short rods that have flat areas ground on opposite sides. These flat

Jan 1, 1947

By T. F. Archbold, W. H. King

THE diffusivities of gold in polycrystalline copper have been determined in the temperature range from 700° to 1000°C by the utilization of the neutron-activation method. Martin, Johnson, and ~saro' used this method for their investigation of the diffusion of gold into copper at 375° and 550°C for 59 days in order to circumvent the experimental difficulties imposed by the 2.7-day half-life of Au-198. They employed the conventional technique of depositing Au-198 on copper specimens for short-time dif-

Jan 1, 1965

NEW YORK SECTION ALLEN H. ROGERS, Chairman, H. C. PARMELEE, vice-chairman, FOREST RUTHERFORD, Vice-chairman, W. S. DICKSON, Secretary, 71 BROADWAY, NEW YORK, N. Y. J. E. JOHNSON, JR. F. T. RUBIDGE, Treasurer, P. G. SPILSBURY A meeting of the New York Section was held at The Machinery Club on Friday evening, Oct. 4, 1918, The Chairman, Allen H. Rogers, presiding. The CHAIRMAN.-MOST of us, I suppose, have been affected more or less by The request of The Fuel Administration that we leave our automobiles standing in The garages on Sundays. We shall all be interested in hearing about The situation that has called forth This, request, and The Oil Administrator, Mr. Requa, has kindly come from Washington to Tell us about it. MARK L. REQUA.-I am very glad To Tell you about the oil problem during This war period. The United States is supplying by far The greater part of all The petroleum products consumed in Great Britain, France and Italy. In addition To This, we have had To supply a marked increase in our domestic consumption, not only of The refined products, but of fuel oil as well. The combination has put a strain on The oil industry, which it is very difficult To meet. The oil companies, being under contract, had no option as To who should get Their oil first, and They were delivering pro rata To everybody; manufacturers of furniture were getting oil with The same regularity as Those who were making aeroplanes or munitions, and The oil companies felt that something should be done. The first order with which I had. anything To do was The priority list for The delivery of fuel oil. That list contained 12 classifications, beginning with bunker fuel and railroads, and you will realize The complexity of The situation when you hear that munitions plants are in class 11. The priority list held during The winter, but transportation became so bad, because of The number of ships that were Taken for trans-Atlantic use, that some of The oil companies were not able To deliver more Than about 60 per cent. into class 5, and nothing beyond that point. To add To the Troubles, the Tank-car mileage fell off. The average for 1917 was about 36 miles per car per day. in January, 1918, it dropped To about 8 miles, and it must have been nearly zero in The early part. of February. Because of The extremely severe winter, furthermore, pipe lines were not delivering anywhere near Their normal capacity. A new priority list has recently been promulgated, introducing a few slight changes. Natural gas has been brought under its provisions, and it has been extended To include The Pacific Coast, which was not considered necessary last winter. The situation in The gas industry is not satisfactory; it is estimated that There will be a decrease of 10 To 20 per cent. in The quantity of natural gas available This winter, as compared with last winter.

Jan 11, 1918

By AIME AIME

THE 140th meeting of the Institute will be held in the Engineering societies Building, 'New York, Feb.: 16-19, and one of the most important features, one which cannot be reduced to text in the TRANSACTIONS, will be the opportunity to renew old friendships and make new friends, to talk things over -to orient one's self in these troublous .times. There will be daily get-together luncheons for all, luncheons and dinners for specialized groups, an informal dance, the annual reception and banquet, and a smoker. And such a smoker! It starts with dinner at .dinnertime, shows signs of cabaret, turns smoker, and then goes entertainment-all for the price of one. This year one can stay long after 11 o'clock-there will be time and opportunity to amble around and meet everyone present. The formal program is rapidly rounding into shape. The annual business meeting will -be held on Tuesday morning and the banquet will be at the Commodore. The four Divisions and the various, Technical Committees are arranging their sessions. and scheduling for these a long list of significant papers. A .feature of the meeting will be a number of round tables on timely subjects.

Jan 1, 1931

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.'-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4'5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,'-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By Donald A. Brobst

The minerals barite (BaSO4 barium sulfate) and witherite (BaCO3 barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1973 consumed at least 80% of the world's produc¬tion of 4.4 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The re¬maining 20% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity fill¬ing, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favor¬able for the discovery of new deposits of com¬mercial value. Witherite is much less common and abun¬dant than barite, although it is more desirable in many ways as a raw material for the pro¬duction of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir condi¬tions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemi¬cally, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite ho¬mogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber in¬dustry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and li¬noleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other sub¬stances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weight down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1975

By G. W. Thompson

G. W. THOMPSON,* Brooklyn, N. Y.-This subject has two aspects, neither of-which can be ignored: these are the economic aspect and the technical aspect. Under ordinary conditions, economic law will take care of the conservation of tin. Under present conditions it seems desirable that economic law should still be permitted to operate as far as is practicable. It is true that this law operates rather slowly, and that under war conditions it cannot be depended upon to give our Government the supply it immediately needs. There should, therefore, be a designation of the essential industries by the Government, and tin should be supplied for those needs, letting the non-essential industries take what is left. At the same time, information ought to be forthcoming as to how tin can be conserved; with tin selling at 80 c. per pound, more or less, it is to the interest of every consumer to get the best information he can as to how he can save tin. Economic law would properly punish those who do not study their own interests in this way. I deprecate, therefore, any centralized socialistic effort toward avoiding penalties through failure to observe and obey economic law. In saying this, however, I am not unmindful that it is desirable for our Government to take such control of the tin situation as may be necessary to the prosecution of the war, practically regardless of the effect of such action upon individual industry, which should studiously seek to adjust itself to the new condition. The Government should promulgate such technical information as it can collect, showing how tin can be conserved, and should urge upon every consumer the exercise of his common sense in self-protection. There is very little danger of any one attempting to hoard or corner tin, in the present state of the market. Most consumers will be glad to live from hand to mouth, covering their sales by purchases, or vice versa. As to the technical aspects: Tin and tin alloys are used to give certain practical and also certain artistic results. The practical factors are those involved in proper adhesion, continuity of surface, protection, the right degree of hardness, proper working qualities, etc. The artistic results are those that appeal purely to the eye or to our cultivated sense of what is desirable. There is no doubt that a great deal of tin could be saved if there were not a demand for certain pleasing effects. How can this saving be brought about? The users of tin hearing alloys are not the only ones involved in this question. The manufacturers of solder and babbitt have for a long time sought to give certain appearances to their fabricated bars and ingots in order to make them more salable. The user of a solder is very apt to judge of its working qualities by the appearance of the bar; the same thing is true with regard to babbitts. Under ordinary conditions, manufacturers are justified in trying to

Jan 12, 1918

PROF RICHARD ÅKERMAN Stockholm, Sweden DR FRANK DAWSON ADAMS Montreal, Canada PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HADFEILD London, England HERBERT C. HOOVER Leoben, Austria ROBERT W. HUNT Chicago, ILL JAMES FURMAN KEMP New York, N.Y. PROF HENRI LOUIS LE CHATELIER Paris France EZEQUIEL ORDONEZ Mexico City, Mexico ALEXANDRE, POURCEL Paris, France PROF RICHARD H, RICHARDS Boston Mass. JOHN E. STEAD Middlesborugh, England PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia PROF TSUNASHIRO WADA Tokyo, Japan CHARLES D WALCOT Washington D.C.

Jan 1, 1923

By C. R. Ince

THE term "differential flotation" is used to denote a flotation operation in which separation is effected between two or more minerals of the same class; e. g., lead sulfide from zinc sulfide, pyrite from blende, chalcopyrite from pyrite, chalcopyrite from blende. At present, so far as published work shows, there seem to be two theories as to the mechanics of differential flotation. The earlier and more generally accepted theory is that the so-called depressing agents alter the surface of one or more of the sulfides in the ore, either by chemical action or adsorption, so that it is no longer amenable to flotation, but that these depressed sulfides can be revived, after the unaffected sulfide has been floated, by reagents which react chemically with the altered surface and make it amenable to flotation. More recently, Professor Taggart1 has advanced the theory that slime adsorption is an important factor in differential flotation. He believes that, with the proper use of a class of agents, which he calls .dispersion agents and which include practically all the depressing agents, one can cause the slime to adsorb differentially on sulfide surfaces. A gangue-slime coated sulfide surface will act as a gangue particle and will not float. If, subsequently, an agent that will remove the gangue-slime coating is added, the sulfide again assumes its original surface and can be floated as an ordinary sulfide. This-is the basis of the slime theory of differential flotation. Timber Butte mill at Butte, Mont., is a typical lead-zinc flotation concentrator. Neihart ore, chosen for investigation in this work, is one of the custom ores treated at that mill. Practice at Timber Butte mill in February, 1928, was as follows: A combined lead-zinc concentrate was first made using 0.2 lb. per ton on the ore of potassium xanthate and 0.03 lb. per ton of Cleveland Cliffs oil after 1.5 lb. per ton of lime and 1 lb. per ton of calcium chloride has been added just before the ball mill. The concentrate was then thickened to 70 per cent. solids. Potassium cyanide to the amount of 0.3 lb. per ton and zinc sulfate in the quantity of 0.5 lb. per ton were added to the thickened pulp and the whole

Jan 1, 1929

By C. R. Ince

The term "differential flotation" is used to denote a flotation operation in which separation is effected between two or more minerals of the same class; e. g., lead sulfide from zinc sulfide, pyrite from blende, chalco-pyrite from pyrite, chalcopyrite from blende. At present, so far as published work shows, there seem to be two theories as to the mechanics of differential flotation. The earlier and more generally accepted theory is that the so-called depressing agents alter the surface of one or more of the sulfides in the ore, either by chemical action or adsorption, so that it is no longer amenable to flotation, but that these depressed sulfides can be revived, after the unaffected sulfide has been floated, by reagents which react chemically with the altered surface and make it amenable to flotation. More recently, Professor Taggartl has advanced the theory that slime adsorption is an important factor in differential flotation. He believes that, with the proper use of a class of agents, which he calls dispersion agents and which include practically all the depressing agents, one can cause the slime to adsorb differentially on sulfide surfaces. A gangue-slime coated sulfide surface will act as a gangue particle and will not float. If, subsequently, an agent that will remove the gangue-slime coating is added, the sulfide again assumes its original surface and can be floated as an ordinary sulfide. This is the basis of the slime theory of differential flotation. Timber Butte mill at Butte, Mont., is a typical lead-zinc flotation concentrator. Neihart ore, chosen for investigation in this work, is one of the custom ores treated at that mill. Practice at Timber Butte mill in February, 1928, was as follows: A combined lead-zinc concentrate was first made using 0.2 Ib. per ton on the ore of potassium xanthate and 0.03 lb. per ton of Cleveland Cliffs oil after 1.5 lb. per ton of lime and 1 lb. per ton of calcium chloride has been added just before the ball mill. The concentrate was then thickened to 70 per cent. solids. Potassium cyanide to the amount of 0.3 lb. per ton and zinc sulfate in the quantity of 0.5 Ib. per ton were added to the thickened pulp and the whole

Jan 1, 1930

By John W. Cahn

The spinodal has long been regarded as a limit beyond which a homogeneous phase could no longer be metastable. But only recently has it become apparent that a phase beyond the spinodal would decompose by simple diffusional clustering mechanism quite different from the nucleation and growth mechanisms encountered for metastable phases. The theory of spinodal decomposition, which is based on the diffusion equation modified by thermodynamic requirements , is phenomenological, and each parameter can be measured by independent thermodynamic or diffusion experiments. The details of the theory have been carefully verified in a number of simple systems. It appears that the spinodal mechanism is commonly encountered in clustering reactions in solids and glasses. HISTORICAL INTRODUCTION The understanding of the earliest stages of precipitation in alloys has been the subject of three prior Institute of Metals Lectures. In 1932 Paul ~erica' reviewed the puzzling evidence that hardening of duralumin is completed before precipitation of CuAlz takes place and suggested that hardening occurs when the copper atoms "assemble in random groups on lattice positions of the duralumin, not of the CuAlz lattice". He called these random groups knots. This modification of his dispersion hardening theory seemed to fit all the facts, but Merica worried that the required diffusion "is just the reverse of what we deem normal; although quite spontaneous, it proceeds uphill, if you please". The reality of Merica's knots was quickly confirmed by Guinier's' and preston's3 X-ray work and these knots are today known as G.P. zones in their honor. Theoretical justification for uphill diffusion was also quickly provided by Becker and Dehlinger~ who noted that the diffusion coefficient could be negative in certain regions of phase diagrams. The boundaries of such regions could be described by a 90-year-old thermodynamic concept first described by ~ibbs' in 1877 as a limit of metastability for fluid phases, which by 1890 had received the name spinodal (see Appendix A). Spinodal in fluids is as old as nucleation theory. Both appear for the first time in the same paper by Gibbs who called the spinodal the limit of metastability. For the first 50 years, nucleation theory was forgotten and the spinodal was extensively treated in every good thermodynamics textbook.81Q The idea was simple and logical and it was accepted as part of a rigorous thermodynamic development of metastable phases, and for a while it was extensively investigated theoretically.

Jan 1, 1969

By W. H. Adams

One of the most attractive subjects for technical writers is the gigantic industry of the manufacture of sulphuric acid. This is no doubt, natural when we take into account that it has grown in this country during the past twenty years, from a production of 60,000 tons in the year 1867, to that of nearly 450,000 tons in 1887. We may well excuse much of the literature which but repeats the same old story, as it serves to bring to the public notice, at proper intervals, the hidden resources of our land; and this constant application of essential truths will sooner or later be the means of freeing us from dependence upon the Old World for necessary chemical products. The present increase in manufacture of this acid in the United States is almost wholly from pyrites ores, which we have in unlimited quantities close at hand. The largest consumption of such acid is for treatment of other native products, petroleum, rock-phosphates, etc.; and, considering the knowledge we have gained during the past twenty years, it is safe to say that the industry is but fairly established, and the causes which have operated to place us in our present proud position are but natural incentives for a further growth and an increased consumption of the many other undiscovered or undeveloped resources of our American soi1. In one of his earlier editions Muspratt says: " It would seem that the manufacture of sulphuric acid, though as extensively carried on as any other business, yet seems to be the least understood; and the ignorance of some manufacturers appears to be only equalled by that of writers, who, in their description of the production of this acid, give figures of apparatus, and vaunt as improvements, things which have been exploded for years. It is possible to find in the works of eminent men drawings of apparatus, for the production of sulphuric acid, which never could possibly have worked one day—some, in fact, could never have worked at all."

Jan 1, 1888

By I. R. Kramer

The effect of the specimen diameter, d, on the flow stress, cra of polycrystalline aluminunz (99.997) was studied. The increase in the flow stress could be accountedfor by the increase in the surface layer stress, with decreasing specimen diameter. Both , and a, were found to be proportional to For the smaller-dianzeter specimen (< 0.033 in.) at strains less than aboul 0.1, the work hardening of the surface layer was greater than that associated with the bulk of the specimen. At higher strains the work hardening due to the bulk appears to be independent of the specimen diameter. THE increase in the strength of metals with decreasing diameter is well-known; however, an adequate explanation for the cause of the size effect is still lacking. The earliest systematic investigation of size effect appears to be that of Onol who reported that for aluminum monocrystals the resistance to slip at low strains increased as the specimen diameter decreased. A change in the stress-strain curve beyond 0.001 strain was not found. However, Suzuki et a1 .&apos; reported for monocrystals of a brass and copper having diameters in the range of 2 to 0.12 mm that the entire stress-strain curve was raised as the specimen diameter was decreased. The effect of size was most apparent when the diameter of the specimen was less than 0.5 mm. In the discussion of this paper Honey-combe reported a size effect in copper crystals as large as % in. diam. These results are in agreement with those of paterson3 and Garstone et al.4 While the majority of the investigations on size effects was conducted in terms of the variation in the diameter of the specimen, several investigators studied the influence of the specimen geometry. For example, Wu and smoluchowski 5 reported that in aluminum monocrystals the slip system was a function of the specimen dimension in the slip direction. King-man and Green 6 studied the influence of size on the compressive stress-strain relationship of aluminum monocrystals when the ratio of length to diameter was constant. Their specimen diameters ranged from to & in. For specimens oriented for single slip the critical resolved shear stress for the smaller-size specimens increased with decreasing diameter. No effect was observed in the large-size specimens. Specimens having an orientation near the corners of the stereographic triangle did not exhibit a size effect. Apparently, the increase in strength with decrease in the diameter of the specimen is a general phenomenon and has been observed in a brass |T and cadmium as well as in aluminum and copper.&apos; In a series of investigations (for example Ref. lo), it was shown that during deformation a surface layer was formed which imposes a back stress, a,, on the moving dislocations. It is reasonable to predict that this surface layer stress, as, should be a function of the specimen diameter and could possibly account for the flow stress size effect. In fact, experimental evidence will be presented to show that this is the case; i.e., the increase in flow stress with decreasing size is equal to the increase in the surface layer stress, as, with size. In addition, data will be presented on the variation with size of and a* where is the back stress associated with the generation of dislocation obstacles in the bulk of the specimen and a* is the net effective stress acting on the mobile dislocations. A limited investigation was carried out on gold specimens to determine the influence of an oxide film. EXPERIMENTAL PROCEDURE The aluminum specimens were prepared from -in. bar stock (99.997 pct purity). The 0.350- and 0.150-in.-diam specimens were machined directly from the bars while the specimens having a diameter of 0.033, 0.020, and 0.015 in. were prepared by swaging and drawing to 0.04 in. and electropolishing almost to final size. The specimens were prepared with a 2-in. gage length. The specimens were annealed in vacuum (-10-4 Torr) at 350°C for 8 hr. The grain diameter of the specimens in the various specimen diameter groups was 0.08 ± 0.02 mm. Gold specimens of two diameters, 0.14 and 0.03 in., were prepared in a similar way and annealed at 650°C for 8 hr. The grain diameter of the gold specimens was 0.2 mm. After annealing the specimens were electrochemically polished to the final size and tested in an Instron tensile machine at a strain rate, E&apos;, of 10- 3 per min. While it was possible to determine the surface layer stress, a,, in the larger-size specimens by measuring the difference, Aa, between the stress before unloading the specimens and the initial flow stress after removal of the surface layer as outlined in detail in Ref. 10, this method is not applicable for small wires because of the difficulty in obtaining a sufficiently accurate measure of the diameter. The values at the various strains were therefore determined by measuring after the specimen had been annealed at 35°C for 4 hr. It has previously been shown" that the two methods give the same results for a provided that the annealing temperature is low enough to affect only the surface layer and not the dislocation barriers in the bulk of the specimen. For the gold specimens a treatment at 150°C for 16 hr was found to be satisfactory for the determination of by the low-temperature annealing method. EXPERIMENTAL RESULTS Determination of a,, and a,. The stress-strain curves for the various diameter aluminum specimens, plotted in terms of the logarithms of the true stress, and true strain, are given in Fig. 1. These curves represent the average data taken from at least ten specimens at each size. Over the range of strains investigated the curves follow the empirical equation

Jan 1, 1968

K. T. Aust and J. W. Rutter (General Electric Research Laboratory)—We find it difficult to reconcile the activation energies determined by Gifkins with his general conclusion that "migration during both creep and grain growth can thus be treated on the basis of the same model" (that of Lucke and Detert). Gifkins finds the activation energy for grain boundary migration during creep to be 24.5 kcal per rnol and that for grain boundary migration during grain growth to be 7.5 kcal per mol. The calculation carried out by Gifkins of the activation energy for grain boundary migration during grain growth, using the Lucke and Detert model, gives a value of 20 to 24.5 kcal per mol, rather than his experimental value of 7.5 kcal per mol. The theory of Lucke and Detert was developed to account for the rates of migration of grain boundaries in the presence of impurities during grain growth. The theory does not take into account the effect on the boundary migration of another, simultaneous process such as creep deformation and would be expected, therefore, to be applicable only to migration during grain growth. The fact that Gifkins measured a different activation energy for boundary migration during grain growth (7.5 kcal per mol) from that during creep (24.5 kcal per mol), although the specimens were of the same composition, shows clearly that such an effect exists under his experimental conditions; the presence of a simultaneous creep deformation markedly affects the boundary migration process in comparison with what would be observed under the same conditions but without the creep deformation. The failure of McLean&apos;s equation (Eq. [4] of Gifkins&apos; paper) to give a satisfactory dislocation density difference for boundary migration during creep is not surprising, since the activation energy which must be used in this equation refers only to the elementary atom transfer process of grain boundary migration. This activation energy value is approximately 6 kcal per mol for zone-refined lead, as determined in both the grain boundary migration experiments of Aust and Rutter31, 32 and the grain growth experiments of Bolling and Winegard.33 Using this activation energy value, McLean&apos;s equation gives reasonable agreement with observed migration rates for grain boundaries moving free of the influence of impurities.31, 32 The value of 24.5 kcal per mol is probably associated with the presence of impurity atoms, as Gifkins suggests. It should be noted, however, that this value was obtained using lead of only one composition and measurements at only two temperatures. The work of Aust and Rutter3"&apos; on the effects of tin, silver, and gold on grain boundary migration in zone-refined lead in the temperature range from 320" to 200°C, as well as the work of Bolling and Winegard34 on the effect of silver and gold on grain growth in zone-refined lead, shows that the measured activation energy is markedly dependent upon the kind and amount of solute present. Gifkins&apos; work does not permit evaluation of the effect of the 8 ppm of impurities other than oxygen present in his specimens. One incidental point: the symbols used to designate the experimental points of Fig. 6 appear to be in incorrect order in the figure caption. As the caption is printed, it would indicate that larger grain sizes were obtained after annealing at 47°C than at 100°C, which does not agree with the text (point M, p. 1019). Finally, it seems clear from Gifkins&apos; results that any serious attempt to determine whether grain boundary migration and grain boundary sliding during creep occur with the same activation energy, as Gifkins suggests and McLean rejects, must take into account the effects of impurities on these two processes, Although the work of Weinberg35 indicated that adding small amounts of copper, iron and silicon to aluminum did not affect the grain boundary shear behavior, it should be noted that his starting material contained approximately 60 ppm of impurities. Gifkins&apos; results indicate impurity effects at an impurity level of 8 ppm, suggesting strongly that the most significant impurity range to be investigated lies substantially below that value. R. C. Gifkins (author&apos;s reply) — As Drs. Aust and Rutter suggest, the results under discussion may have to be reinterpreted in the light of their own work on grain boundary migration, which was not available to me when the paper was written. Because of their work, Aust and Rutter attach more importance than I did to the activation energy for grain boundary migration during annealing (7.5 kcal per mol) obtained from a "direct" plot of log-rate against the reciprocal of absolute temperature. At the time it was obtained, this value seemed rather low, although it was similar to the value obtained by Bolling and Winegard.36 It was then, and still is, difficult to accept this value because of the low value of the index in the power law for grain growth, which seemed to indicate the influence of impurities. It was also concluded that the low value of the activation energy might have arisen from the manner of selecting rates of grain growth which were truly comparable at the two temperatures. There were many other indications in these experiments and those on recrystallization during creep3? that an impurity, probably oxygen, was of importance. The model for grain-boundary migration which Lucke and Detert had proposed was an obvious possibility and its use yielded an activation energy for boundary migration during annealing of 20 to 25 kcal per mol.

Jan 1, 1961

By L. G. Austin, P. T. Luckie, R. R. Klimpel, R. S. C. Rogers

1. INTRODUCTION The Bond method(1.2) for sizing tumbling ball mills has been used successfully for many years. The primary purpose of the Bond calculation is to predict the mill size and mill power to give a desired capacity (Q tph) from a wet overflow ball mill in normal closed circuit operated with a circulation ratio of 2.5. The input to the calculation is the make-up feed size characterized by the 80%-passing size in micrometers (xG), the desired circuit product size characterized by the 80%-passing size (xQ), and an empirical grindability number (the standard Bond Work Index) determined by a standard test. A series of empirical correcting factors(2) are used to convert the results to open-circuit or dry grinding in grate discharge mills. The Bond method has two major engineering advantages: (i) it is very simple; (ii) experience has shown that it works for many circumstances, as a reasonable approximation, because it is based on direct conversion of test data to results measured on industrial mills. There are four main disadvantages of the Bond method. First, there will be a range of error for any specific mill and material and set of operating conditions because the method does not explicitly include several variables which are obviously important: (i) recycle ratio and classifier efficiency (ii) mixture of ball sizes in the mill (iii) variations of residence time distributions with mill geometry and slurry density (iv) lifter design (v) slurry rheology (vi) different underfilling or overfilling of the mill as flow rate is changed. Second, the Bond method explicitly assumes that specific grinding energy E is not a function of ball load, whereas industrial practice and laboratory tests(3) show that the specific grinding energy (to go from a specified feed to a specified product) is less for lower ball loadings than the ball loading for maximum mill capacity. Third, the method uses only the 80% passing size of circuit feed and product to characterize the size distributions, whereas mill capacity in general must depend on the shape of the feed size distribution and the product size distribution. The prime example of this is the use of the reverse closed circuit which removes some fraction of the make-up feed before it is

Jan 1, 1982