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By R. S. French, W. R. Hibbard

M. Balicki—As one who some years ago spent much time searching for an alloy with high thermoelectric power that would be suitable for heat energy-electric energy converter based on the principle of a thermoelectric pile, I would like to make a few comments touching upon that aspect of this excellent paper. The specifications which one of the authors has formulated so aptly do not appear to me as complete, and I would like to add to them the following two demands: (1) Melting point not less than 500°C and (2) elongation on 2 in. at least 5 pct. Condition 1 would insure good thermodynamic efficiency of the pile by permitting a reasonably high temperature of the hot junction and at the same time making it suitable for such application as salvage of vast amounts of energy which is lost in the form of sensible heat of waste gas leaving industrial and other furnaces. Condition 2 is also a very important one; particularly, because of the fact that all elements and alloys which exhibit attractive thermoelectric properties seem to be as a rule very brittle. The design, erection, and maintenance of a pile incorporating a brittle material in one of the most crucial parts of the converter would be a very difficult and costly affair indeed. To illustrate this point I may mention great difficulties I encountered when trying to make thermocouples of silicon. Casting of 1/4-in. rods in iron or graphite mould yielded only broken pieces which had to be welded into a bar. Such a bar had to be handled very carefully during the determinations. Raising the molten silicon by vacuum into a silica tube and solidifying it there solved the problem of stability as well as that of electrical insulation of a bar. On tests this bar (98.5 pct Si) showed dE/dT = — 275.5 microvolts per degree C vs. copper. Thermocouples made of this grade of silicon and pure nickel developed 0.39 v when temperature of the hot junction was approximately 1000°C. The possibility Dr. Gonser has mentioned of trying to impart to metals good thermoelectric properties by alloying them with silicon, has been considered. The preliminary survey which I have made was, however, disappointing. Perhaps, it will be advisable to record the results obtained (table VI), as this might save repetition of search in fields already covered.

Jan 1, 1951

By Richard McCaffery

THIS paper considers certain aspects of the acid Bessemer process, particularly in its relations to the duplex process-that combination in which the pig iron is first desiliconized and decarburized in acid Bessemer converters and then dephosphorized in basic open-hearth furnaces. The acid Bessemer process employs an acid-lined converter and produces an acid slag. The blow is usually thought to eliminate the silicon and manganese as oxides and then to burn off the carbon as carbon monoxide. On account, however, of the relatively large amount of metallic iron present in the converter, compared with the relatively small amount of the impurities it is desired to oxidize, the first reaction in the converter probably is the formation of iron oxide, which dissolves in the bath and acts as an oxygen carrier for the silicon and carbon. As soon as iron oxide is dissolved throughout the bath, the oxidation of silicon commences; but in the early stages of the blow the mass law would indicate that iron oxide must form first, and this oxide probably increases up to some saturation point. The molten metal in the converter from the early stages of the blow right through to its completion remains basic, while the slag produced is siliceous. This fact is shown by the corrosion of the acid bottom and the tuyeres, which is greatest at the tuyere orifice where oxidation is most active and where there is the most iron oxide. Why does this acid bottom corrode? Because it is attacked by a base. The thought, therefore, suggests itself, why not make the bottoms of basic or neutral material?1 As the converter slag is acid, those parts of the converter coming in contact with the slag should be acid; but those parts of the converter that are in contact with the molten metal saturated with metallic oxides should be basic or neutral. Bessemer operators have for some time tacitly admitted this condition, for the blast pressures have steadily increased with the object of keeping the metal in suspension, and so preventing bottom corrosion; if the molten metal were not basic, it would not attack an acid bottom. In addition, the tuyeres are bunched together at the middle of the bottom and a clear space is left around the outside of the bottom; if tuyeres are placed too near the side walls the

Jan 8, 1920

By P. D. Hunt, B. Tani, M. G. Chasanov, R. Schablaske

The Zn-Vphase diagram was studied by thermal. metallographic, X-ray, and sampling techniques. Three ternary phase equilibria were observed: Mutual solid solubilities in vanadium and zinc appear to be negligible. The liquidus line is retrograde from 670° to 756°C. 1 HE only information in the literature relating to the Zn-V system was a study of corrosion of vanadium by liquid zinc' and an examination of the effectiveness of zinc coatings in protecting vanadium-base alloys from oxidation at high temperatures.2 Establishment of the Zn-V phase diagram was undertaken as part of a study of transition metal solubilities in liquid metal solvents. Chemical, metallographic, thermal, and X-ray diffraction analyses were used to determine the diagram. MATERIALS AND EXPERIMENTAL PROCEDURES Vanadium (99.86 pct) in the form of powder and small chips was employed. Stick zinc (99.99 pct; major impurities: 10 to 15 ppm Pb and 20 ppm Cu) was used in the liquidus determinations and thermal analyses; zinc powder (98.80 pct) was used to prepare intermediate compositions. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The apparatus and sampling techniques were similar to those described by Martin, et al.3 The entire metal sample was dissolved to preclude analytical errors due to segregation on cooling. Vanadium was determined amperometrically, using iron (11) as the titrant,4 to an estimated accuracy of 1 pct. Standard techniques of thermal analysis were employed to examine alloy specimens contained in alumina crucibles under helium. Heating and cooling rates were about 1°C per min. At least five heating and cooling cycles over the range 420° to 700°C were performed for each of two Zn-15 pct V alloys. A Zn-0.2 pct V alloy was used in the determination of the eutectic temperature. The separation of intermediate phases from zinc-rich alloys was carried out by selective leaching with ammonium nitrate solutions. For further investigation of intermediate phases 1/4 in. diam powder compacts were prepared by pressing at 80,000 psi and were annealed in argon at 415" to 450°C for 10 days. Larger quantities of intermediate phases were prepared in sealed tantalum capsules heated in a rocking furnace. Temperatures were determined to an estimated accuracy of 0.5°C with a Pt/Pt-10 pct Rh thermo-

Jan 1, 1963

By W. H. Eardley

It is increasingly evident that the excellence of blast-furnace operation to a great extent depends upon the preparation of the products fed into the furnace. The preparation of these products is carried on largely in the roasting and sintering departments. Prior to the building of flotation plants in Utah and other western states for the treatment of lead-zinc ores, the gravity concentrates received at the Midvale smelter amounted to about 4000 tons per month, containing 24 per cent. lead and 10 or 11 per cent. zinc. This product was about 20 mesh—that is, 45 per cent. of it would be plus 20 mesh and the balance minus 20 mesh. About 1000 tons of pyrite per month, containing 5 per cent. lead and 10 per cent. zinc, was also received. These products were sent to the multiple-hearth roasters for calcining, after which they were sent to the Dwight-Lloyd machines for sintering with other ores. The sintering charge passed over the machines but once. The first flotation products received consisted of a wet, sticky, muddy mass, containing a large amount of moisture, up to 19 or 20 per cent., and it was almost impossible to feed them with any degree of regularity, if at all, through our standard feeders; but the amount of flotation product received during the first year or so was relatively small and it virtually lost its identity by being mixed with a large amount of jig and table concentrates. As the quantity of flotation products increased, more efficient filtering was accomplished and the moisture greatly reduced. Flotation Products Received At the present time the Midvale plant receives about 4300 tons per month of flotation product running 60 per cent, lead and 4.5 per cent. zinc, 85 per cent. of which is minus 200 mesh and contains about 8 per cent, moisture; and 4000 tons per month of pyrite of similar fineness, running about 2 per cent. lead and 3.5 per cent. zinc, containing about 10 per cent, moisture. The lower moisture greatly reduces the difficulties of handling, making it possible to run a 100 per cent. flotation feed on a multiple-hearth furnace without serious mechanical troubles. The calcine, however, would contain nodules and balls of unroast,ed concentrates, sulfur elimination

Jan 1, 1928

By E. G. Dean

A method of top slicing has been devised at the Miami Copper Co.'s mine at Miami, Aria., which differs radically in some ways from the customary methods of top slicing. The area of that section of the orebody in which top slicing is used is about 800 ft. square. The ore, while for the most part soft, is, nevertheless, considerably harder than the capping. The latter is siliceous, seldom containing any clay or other binding material, and breaks into fine particles so that it runs like sand if given the opportunity. Because of these facts, and because the ore is above the average grade of the mine ore, it has been mined by top slicing. Haulage levels are opened up 150 ft. apart, vertically, with two sub-levels between at 50-ft. intervals, to facilitate the putting up of ore chutes. These sublevels are used during slicing for distributing air in the ventilation system. On the haulage level the drifts are spaced on 50-ft. centers, and raises along these drifts are also spaced on 50-ft. centers, except the incline raises as hereafter noted. The raises are cribbed where necessary. Where the wear will be excessive, 1/4-in. iron plates are spiked to the top of every third set of cribbing, for its protection. When top slicing was first used, an attempt was made to carry a slicing face from fifty to several hundred feet long. Timber and other supplies were brought in through long drifts from an auxiliary shaft. Great difficulty was experienced in keeping these drifts open, the side pressure breaking the posts and the top weight breaking both caps and posts. Furthermore, the men could not work efficiently while these drifts were being repaired. The slicing faces advanced irregularly, due to varying conditions, and in many ways the results were not all that could be desired. It was then decided to divide the slicing area into blocks 200 ft. square and this was later changed to 250 ft. square. At the center of each block a two-compartment raise is put up as a supply raise, the compartments being 2 ft. 6 in. and 4 ft. by 4 ft. 4 in., the smaller being used as a manway. Station sets of 12 by 12 timber with

Jan 1, 1917

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.' Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.' The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By Max Roesler

W. L. CUMINGS,* Bethlehem, Pa. (communication to the Secretary+). -In this discussion of Mr. Roesler's paper, I shall follow Kemp in using the term "granite" to refer to the acid rock called syenite by Kimball. Diorite, as I understand it, is the dark basic rock invariably closely associated with the orebodies. The types of rock of intermediate composition, mainly intrusives, are not under discussion. It is difficult for me to conceive that this granite is the ore-bearing agent, for the following reasons: 1. No isolated orebodies in the granite are known. It would seem that if this rock is the mineralizer, some small bodies, or at least patches and small masses of ore so situated would exist. 2. In 1909 the writer conducted explorations on the Pequena and Grande claims about 1 mile north of West Mine No. 5. This work was done after a very careful magnetic survey had shown a large and uniform area of attraction. As exploration progressed, it became evident that in this case the magnetic attraction was due to disseminated magnetite. Much ore of 40 per cent. Fe was found, but very little commercial ore was shown up. This ore was entirely in the diorite and no granite outcrops are near. The occurrence could easily have been described as "ore formation but very little ore." I cannot conceive how a remote granite intrusion could impregnate a diorite mountain with 40 per cent. of Fe, and prefer to believe that this 40 per cent. of iron was in its real home, rather than in a sort of dioritic "boarding house" after having been evicted by granitic parents. 3. The Ocaña mine, which has produced nearly 500,000 tons, shows no evidence that the granite is the mineralizer. This is admitted by Mr. Roesler on p. 1827. 4. I believe it will not be disputed that all the iron-ore deposits extending along the south coast for 60 or 70 miles are of a similar origin. Evidence available at other points might properly be referred to in discussing the article under review. At the La Plata mines, about 60 miles west of Santiago, the writer has also made explorations. No granite is in evidence. At one point in the bed of a creek is a small body of magnetite about 10 ft. long, entirely surrounded by a hard fresh diorite. To me

Jan 3, 1917

By I. I. Gardescu

Rumania produced during 1936 some 62,500,000 bbl. of oil. Of this production, 99 per cent comes from an area running east and west along the southern foothills of the Carpathian Mountains just north of Bucharest. This almost rectangular area measures 20 by 40 miles and is located in the districts of Dambovita and Prahova between the cities of Targovigte to the west and Mizil to the east. The remainder of the production is about evenly divided between the oil fields north and east of Mizil in the Buzh district and those to the north on the eastern flanks of the Carpathian Mountains in the district of Baciiu. The Transylvanian Basin to the north and west of the Carpathian Mountains has produced to date only dry gas from its numerous salt domes. Bucsani Field The Bucgani oil field produced 15,600,000 bbl., or 25 per cent of the total production of Rumania in 1936. Bucgani is a deep-seated salt dome 7 miles south of the old Moreni oil field. A slight surface doming, not dissimilar to the topography observed on some of the oil fields of the Californian basin, called attention to the area. It is the southernmost oil field and, together with the deep-seated and prolific Boldesti field, points to the great oil possibilities of the deep-seated domes along the northern edge of the Rumanian plains south of the Carpathian foothills. The Government is the principal owner of the oil and gas subsurface rights in the areas south of the foothills. The acquisition of leases by the operating oil companies may be made either by application for an exploration permit, the company being assigned part of the acreage in case of successful wildcatting, or, if the area has already been declared as proven territory, through competitive bidding. A block of 164 acres was auctioned recently for $200,000, or $1200 per acre. The largest producer in the Bucgani oil field is the Steaua Romana, which produced 39.5 per cent of the total for the field. The Steaua Romana is a post-war company and 50 per cent of its shares are owned by the British Steaua and the Steaua Franpaise and the other 50 per cent by a group of Rumanian banks and by the Government. The Colombia,

Jan 1, 1937

By W. H. Eardley

IT IS increasingly evident that the excellence of blast-furnace operation to a great extent depends upon the preparation of the products fed into the furnace. The preparation of these products is carried on largely in the roasting and sintering departments. Prior to the building of flotation plants in Utah and other western states for the treatment of lead-zinc ores, the gravity concentrates received at the Midvale smelter amounted to about 4000 tons per month, containing 24 per cent. lead and 10 or 11 per cent. zinc. This product was about 20 mesh-that is, 45 per cent. of it would be plus 20 mesh and the balance minus 20 mesh. About 1000 tons of pyrite per month, containing 5 per cent. lead and 10 per cent. zinc, was also received. These products were sent to the multiple-hearth roasters for calcining, after which they were sent to the Dwight-Lloyd machines for sintering with other ores. The sintering charge passed over the machines but once. The first flotation products received consisted of a wet, sticky, muddy mass, containing a large amount of moisture, up to 19 or 20 per cent., and it was almost impossible to feed .them with any degree of regularity, if at all, through our standard feeders; but the amount of flotation product received during the first year or so was relatively small and it virtually lost its identity by being mixed with a large amount of jig and table concentrates. As the quantity of flotation products increased, more efficient filtering was accomplished and the moisture greatly reduced. FLOTATION PRODUCTS RECEIVED At the present time the Midvale plant receives about 4300 tons per month of flotation product running 60 per cent. lead and 4.5 per cent. zinc, 85 per cent. of which is minus 200 mesh and contains about 8 per cent. moisture; and 4000 tons per month of pyrite of similar fineness, running about 2 per cent. lead and 3.5 per cent. zinc, containing about 10 per cent. moisture. The lower moisture greatly reduces the difficulties of handling, making it possible to run a 100 per cent. flotation feed on a multiple-hearth furnace without serious mechanical troubles. The calcine, however, would contain-nodules and balls of unroasted concentrates, sulfur elimination

Jan 1, 1928

By B. D. Cullity, J. T. Norton, M. Telkes

M. Balicki—As one who some years ago spent much time searching for an alloy with high thermoelectric power that would be suitable for heat energy-electric energy converter based on the principle of a thermoelectric pile, I would like to make a few comments touching upon that aspect of this excellent paper. The specifications which one of the authors has formulated so aptly do not appear to me as complete, and I would like to add to them the following two demands: (1) Melting point not less than 500°C and (2) elongation on 2 in. at least 5 pct. Condition 1 would insure good thermodynamic efficiency of the pile by permitting a reasonably high temperature of the hot junction and at the same time making it suitable for such application as salvage of vast amounts of energy which is lost in the form of sensible heat of waste gas leaving industrial and other furnaces. Condition 2 is also a very important one; particularly, because of the fact that all elements and alloys which exhibit attractive thermoelectric properties seem to be as a rule very brittle. The design, erection, and maintenance of a pile incorporating a brittle material in one of the most crucial parts of the converter would be a very difficult and costly affair indeed. To illustrate this point I may mention great difficulties I encountered when trying to make thermocouples of silicon. Casting of 1/4-in. rods in iron or graphite mould yielded only broken pieces which had to be welded into a bar. Such a bar had to be handled very carefully during the determinations. Raising the molten silicon by vacuum into a silica tube and solidifying it there solved the problem of stability as well as that of electrical insulation of a bar. On tests this bar (98.5 pct Si) showed dE/dT = — 275.5 microvolts per degree C vs. copper. Thermocouples made of this grade of silicon and pure nickel developed 0.39 v when temperature of the hot junction was approximately 1000°C. The possibility Dr. Gonser has mentioned of trying to impart to metals good thermoelectric properties by alloying them with silicon, has been considered. The preliminary survey which I have made was, however, disappointing. Perhaps, it will be advisable to record the results obtained (table VI), as this might save repetition of search in fields already covered.

Jan 1, 1951

By Jesse O. Betterton

In the Parkes process of lead refining, after desilverization has been completed by means of zinc additions, there will remain in the lead from 0.5 to 0.6 per cent zinc. At this stage in the refining practically all impurities are reduced to refined lead specifications except zinc and antimony. All excess of copper and nearly all the arsenic goes out with the silver. Silver remaining should not exceed 0.1 oz. per ton. It thus remains only to remove zinc and antimony to produce refined lead. The older practice was to complete refining by means of oxidation processes in reverberatory furnaces. Essentially this consisted of heating the lead to 1200' to 1300" I?. and allowing it to come in contact with a considerable excess of air passing through the furnace, or accomplish the same result by blowing the lead with steam by means of pipes introduced for that purpose, at the same time allowing air to enter the furnace. Usually some procedure involving alternate oxidation and reduction with fine coal or coke was employed in order to reduce the weight of dross or skim finally removed from the furnace. This practice had many elements of weakness in that the main flour of lead, after the preceding expensive operations had been performed, and the whole refining process nearly completed, was subjected to an operation at a comparatively high temperature, which involved much lead loss if the furnaces were not on bags, and the production of 3 to 5 per cent of the weight of the lead as dross or skim, which had to be resmelted and the lead either refined or produced as antimonial lead. In addition, the operating expense of the process was a considerable item. The process of dezincing with chlorine was developed as a substitute for the foregoing described oxidation process, and finally resulted in such advantages as nearly equal operating costs, a practical elimination of the lead loss, and the direct production of a very valuable byproduct, zinc chloride, that may be sold as such or retreated for its zinc and chlorine contents, both of which can be reused in the refining processes. Essentially this process consists of circulating the lead by means of a pump in a kettle through a closed reaction cylinder, gaseous chlorine entering the reaction cylinder with the stream of lead from the pump. Molten zinc chloride is thus produced and is discharged together with

Jan 1, 1937

By Olav Klomstadlien

The lean, but extensive iron ore deposits of the Dunderland Valley north of Mo i Rana, Norway, are the raw material base for Rana Mines, a division of the state-owned A/S Norsk Jernverk steel mill. The iron bearing minerals are magnetite and specular hematite. The magnetite/hematite ratio varies considerably both within each deposit and from one deposit to another. The ore bodies that lend themselves to mining have generally a thickness of 30-60 m grading 30-35% Fe and 0.15-0.25% P. The grain size varies from 0.05 to 2.5 mm. The fine grained ores are hard while the coarse grained ores are soft and easy to grind. The A/S Norsk Jernverk steel mill operates both a sinter and a pellet plant, and this necessitates production of two types of concentrates. The present flowsheet is shown in [Fig. 1]. The crude ore from the pits is crushed in a 1.07-m gyratory crusher with an open side setting of 12.7 cm. The crusher product is transported by rail to the concentrator located 25 km from the mines. The ore is fed by twelve 1.22 X 1.83 m vibratory feeders onto conveyor belts which carry the ore to a surge bin ahead of the autogenous mills. The feed rate is automatically adjusted to maintain a set power load at a level suitable for the ore type being processed. The mills operate in closed circuit with twelve dual-drum screens equipped with a 0.8-mm screen cloth. Oversize is returned by gravity to the mill feed while undersize flows to the gravity separation section which consists of Humphrey spirals in three stages. The ores are very heterogenous and analysis may vary quite considerably. The quantitative need for concentrate in the steel mill may also change rapidly. The process in the concentrator must therefore be easily changed, and consequently alternative process lines have been established. This is indicated with the dotted lines in the flowsheet. Apatite is removed by flotation by fatty acids to give a final sinter concentrate of 63% Fe and 0.020% P or less. Pellet concentrate contains about 65% Fe and less than 0.020% P. The fineness is about 1500 Blain.

Jan 1, 1981

FOLLOWING the presentation at the annual meet-ing of the paper "Recent Developments in Classi-fication," by A. M. Gaudin and W. L. Remick, the discussion presented below took place: H. N. Spicer : I haven't been able to study this paper closely, but I would like to ask 'Mr. Remick something regarding the work done by the mechanical classifier. The screen test given here would appear to show that the classi-fier did very, very poor work. The 44 per cent efficiency calculated from this equation is much lower than any ordinary operation. Nothing is stated regarding the de-tails. of the operation, the slope of the classifier, the dilu-tion, the speed, and such other factors that influence results. I would also like to know something of the material that was worked. The Manhattan schist that I have seen them digging out of the subways is of a flaky nature, so that in any classifier, you might get the factor of fine flakes floating over. Was the same material used in the hydrotator test? The screen tests vary a whole lot. Mr. Remick: You will notice the Dorr classifier han-dled the circulating load. This classifier naturally was run in closed circuit. I should like to be pardoned for quoting from Mr. Bates' paper of last year on "Classifica-tion in the Witwatersrand Mills." In this report only two efficiencies were given for the so-called straight type Dorr classifier. One was 44.6 per cent and the other 61.6. I don't know whether or not an average should be taken for the proper performance. I assume that that test was performed under better conditions, yet the efficiencies av-eraged only 53.1 per cent. I am afraid I am taking the words out of Professor Taggart's mouth, but he has told me that the Dorr classi-fier at Columbia is not the proper size to work with the Hardinge mill with which it is connected. This indicates only the inadvisability of putting commercial sized mat chines in a school laboratory. You cannot, he says, get the proper tonnage from the Hardinge mill to work the Dorr classifier and get the best results. Mr. Bates' results show higher efficiency with the lower capacity. Now, on the other hand, I assume that the classifier described in Mr. Bates' paper was probably run at the proper capacity.. It is a rather puzzling question.

Jan 4, 1927

By Wilhelm Flesch

THE object of development work in the field of gasification is to find a process by which all' fuels, regardless of their individual properties, can be gasified economically. This paper describes the development of the Winkler process. The economy of the gasification process depends not only on the degree of the gasification effect but also, to a decisive extent, on the costs of fuel, production, and installations. Fig 1 shows the relation between fuel costs and gasification efficiency for various types of fuels. Since the fuel cost in the gasification of coke amounts to two thirds of the price of gas, and the thermal unit in brown coal costs only one third of what it costs in coke, it is easily seen how profitably cheap fuels can be gasified, especially if these fuels require minimum preparation and gasification is done in the vicinity of the mines. These possibilities were a great advantage of the Winkler generators, which were installed 20 years ago in the central German brown-coal fields and, at that time, were without rival for the gasification of finely divided fuels. In the Winkler generator (Fig 2), crushed and ground solid fuels were, for the first time, successfully gasified with oxygen and steam on an industrial scale. Unlike the usual processes formerly employed on an industrial scale, this gasification, which proceeds continuously in the glowing, seething fuel bed, makes only extremely low demands on the fuel. The fuel no longer has to be in lumps and abrasion-resistant, but must be capable of reaction and must be fed into the generator in a grain size of 0 to 8 mm. Brown coal or bituminous coal, or their low-temperature cokes, can be gasified in the Winkler generator. Large plants using fuels are operating on an industrial scale in Europe and in Japan. Table 1 shows the results obtained by gasifying these, fuels in Winkler generators. The thermal efficiency of gasification, which is the relation between the calorific value obtained in the gas produced and that of the fuel consumed, gives no indication of the quantity of steam generated in gasification. The generation of steam in the waste-heat boiler of the Winkler generator adequately-covers the steam consumed in gasification. To obtain effective gasification in the Winkler process, combustible mate-

Jan 1, 1953

By A.E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By A. E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By R. F. Mehl, C. E. Birchenall

R. E. Hoffman and D. Turnbull—The authors have presented evidence which they have interpreted as indicating that the rate of self diffusion is not intrinsically more rapid at grain boundaries than within the grain. Grain-size effects which apparently exist are attributed rather to impurities concentrated at the grain boundaries. In view of our own experiments and the existing evidence, we believe that the support for this hypothesis is not convincing. We have in progress an investigation in which the rate of self diffusion of silver is being measured over an extended temperature range in both single-crystal and polycrystalline specimens. The results of the single-crystal experiments and some preliminary data on fine-grained polycrystalline specimens have already been reported:' and it is anticipated that a complete report will be published in the near future. The self-diffusion coefficient of large-grained polycrystalline silver (1 grain per sq mm) has previously been measured by Johnson" between 730" and 940°C. The diffusion coefficients which we have measured in single crystals (210 plane normal to diffusion direction) agree within experimental error with values calculated from an extrapolation of Johnson's curve down to temperatures as low as 500 °C. However, it has been demonstrated that the overall self-diffusion rate in fine-grained polycrystalline specimens (initial grain size of 0.003 cm) becomes measurably larger than the overall rate in a single crystal at a temperature of 600°C, and the discrepancy between the two rates becomes greater as the temperature is further decreased. In fact, it has been possible to obtain satisfactory penetration curves for polycrystalline specimens using the sectioning technique at temperatures as low as 400°C. At this temperature, the penetration is 50 to 100 times greater in the polycrystalline specimens than in a single crystal. Fisher" has developed an analysis whereby the ratio of the rate of the unit diffusion process at the grain boundary to the corresponding rate within the grain can be calculated from the penetration curves and an assumption as to the width of a grain boundary. This analysis applied to our data indicates that the unit process at the grain boundary is faster by a factor of 10' at 475°C when the grain boundary width is taken to be 5. The silver used in most of these experiments was obtained from the Handy and Harmon Co. and listed as 99.97 pct pure. Preliminary experiments on 99.999 pct silver from the Jarrel-Asch Co. indicate a grain-size effect of the same order of magnitude as in the less pure silver. Nominally, these purities are as good, at least, as that of the carbonyl iron used by the authors, but of course if an impurity effect does exist its magnitude might be very dependent upon the nature of both major and minor constituents. The authors have cited the work of other investigators who have found no grain-size effects. Neither Steigman, Shockley and Nix" nor Maier and Nelson8 were able to correlate self-diffusion coefficients of copper with grain size. However, all their measurements were performed at or above 750°C; and on the basis of our work with silver, no grain-size effect would be expected at temperatures above about 0.7 of the absolute melting temperature unless the grain size were exceedingly small. Likewise, in the investigation of the self diffusion of lead by Seith and Keil,14 the lowest temperature at which the diffusion coefficient was measured in polycrystalline specimens was 207°C, which is still sufficiently high so that the lack of a grain-size effect is not surprising. Finally, in those experiments on iron from which they concluded that there was no grain size effect, Drs. Birchenall and Mehl seem to have no information as to the actual grain sizes immediately prior to and following the diffusion anneal. Without this information, we believe that their own experiments offer little support for their hypothesis. F. S. Buffington, I. D. Bakalar, and M. Cohen—The results given in this paper agree in order of magnitude with those tentatively reported by us.27 However, significant differences exist in the two sets of data, and it may be well to make an explicit comparison. The diffusion studies at M.I.T. were conducted on somewhat higher purity iron (99.98 pct Fe) than the grades used by the authors, but this is undoubtedly not the answer. Fig. 4 shows the diffusion results of both laboratories for the gamma phase, omitting the authors' data on the commercial steels, while fig. 5 presents a similar comparison for the alpha phase. The divergence is much more marked in the latter case than in the former. In connection with the M.I.T. determinations, all of the runs in the gamma range and those above 800 °C in the alpha range were conducted with specimens having a relatively thick (0.002 cm) electrodeposit of radioactive iron. This practice minimizes any possible error due to extraneous diffusion that may occur during the heating to and cooling from the operating temperature. An exact solution of Fick's law for these boundary conditions was used in calculating the diffusion coefficients. At a later time, three runs were made below 800°C, using very thin electrodeposits similar to those of the authors, and the points fell considerably below the values expected from the extrapolation of the results based on the specimens with the thick deposits (compare dash-dot line in fig. 5). However, in the runs with the thin deposits, deviations of 100 pct were found between the individual specimens, whereas the maximum deviation with the thick deposits was less than 25 pct. Accordingly, it is not known at the moment whether the M.I.T. points below 800 °C should be given as much weight as those above 800°C. If this were done, the frequency factor would be of the order of 400 cm2 per sec, which is quite high. In other metals, the frequency factor for self diffusion lies between about 0.1 and 10 cm2 per sec. As the points below

Jan 1, 1951

By Phillip E. La Moreaux

Fluoride, generally less than 0.5 ppm, is present in ground water from rocks of Paleozoic age and older, in northern and eastern Alabama. Some of the water-bearing formations in the Coastal Plain area of the State yield water with as much as 6.8 ppm fluoride. IN June 1940, the U. S. Geological Survey, in cooperation with the Geological Survey of Alabama, began a study of the ground-water resources of the part of Alabama where water is obtained from Cretaceous rocks. The purpose of the study was to determine the quality, quantity, occurrence, and availability of ground water in that area. These studies have been expanded to include ground-water investigations in the area of Tertiary rocks, or southern quarter of the State, and certain areas in northern Alabama. The first report issued on these studies was by C. W. Carlston,1 of the Alabama Geological Survey. In the present paper all references to ground-water data for the Cretaceous area are taken from this earlier publication. In 1945, the Dentistry Division of the Alabama Department of Public Health became interested in the correlation of tooth decay and mottled enamel with the chemical quality of ground water used for public supplies in the State. Through a cooperative arrangement between the State Department of Public Health and the Ground Water Division (now Branch) of the U. S. Geological Survey, a report by the author2 was published in 1948. These two reports give accurate information on the occurrence of fluoride in the Coastal Plain of Alabama. At present, only scattered information is available on fluoride in ground water of the crystalline-rock or Piedmont area and for the Paleozoic area of Alabama, but it is hoped that in the future more complete information on the presence of fluoride in ground water in these areas can be collected. Outline of Geology and Ground Water: As described by Adams,3 the State of Alabama includes parts of two major geologic divisions, the Appalachian region and the Coastal Plain. The boundary between these divisions is irregular and is known as the Fall Line of the Atlantic and Gulf Coast States. The Fall Line enters Alabama near Phoenix City, extends westward to Wetumpka, Clanton, and Tuscaloosa, and then swings northwestward to the northwest corner of the State. The Appalachian region in Alabama includes three major provinces, the Piedmont province, the Appalachian Ridge and Valley province, and the Appalachian Plateau province (fig. 1). The rock formations in the Piedmont province in east-central Alabama are mainly of pre-Cambrian age, chiefly crystalline schists and gneisses injected by younger igneous rocks (fig. 1, I). They are faulted and folded and have a complicated structure. These rocks are the oldest and among the most complex rocks in the State. Generally, only small yields of ground water are obtained from rocks in this area. Even though ground water is of great importance for the development of domestic and farm supplies in rural areas and a few small industrial and municipal wells, yields in the area from individual wells generally range from 5 to 25 gpm and rarely exceed 50 gpm. The geologic formations of the Appalachian Ridge and Valley province and the Appalachian Plateau province (see fig. 1, II, and III) are separated on the basis of their structure. These rocks are of Paleozoic age, ranging from Cambrian to Carboniferous, and comprise a succession of formations consisting chiefly of shale, sandstone, limestone, and dolomite, aggregating many thousands of feet in

Jan 1, 1951

ASIDE from the John Fritz Medal, in which the Institute participates through its representation on the John Fritz Medal Board, the Institute itself has five major awards to make annually for excellence in technical papers, as follows: The Robert W. Hunt Medal, The Hadfield Prize, The J. E. Johnson Jr., Award, The Lewisohn Platinum Prize to senior members, and the President's Prize to junior members. ROBERT W. HUNT MEDAL The partners of Robert W. Hunt established a fund which was presented to the Institute at a fitting ceremony on May 27, 1920, to establish an annual medal and a sum of money to be awarded under the following rules: 1. The award shall consist of two prizes; first of a gold medal, second of a sum of money; a certificate to accompany each prize. The money prize shall not be awarded to. a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age. In general it will be understood that the Committee shall award the money prize to the younger men, rather than the medal. 2. The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel. The scope of the term "iron and steel" shall be determined by the sub-committee considering the awards. In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition of the fact that Captain Hunt's main contributions to the industry have been in the improvement of production and quality of material. 3. A sub-committee of three to five including the Chairman of the Iron and Steel Committee, shall be appointed by the iron and Steel Committee annually to adjudge the award subject to approval. 4. The awarding committee shall submit its report to the Iron and Steel Committee at its October Meeting, and the. award be certified to the Secretary of the Institute in time to permit the presentation to be made at the Annual Meeting of the Institute. 5. The recipient of the award shall be designated "The Hunt Medallist." SIR ROBERT HADFIELD PRIZE Sir Robert Hadfield has offered an Institute prize of $1000 for researches with regard to the different forms of combination of carbon in iron and steel. Until within a few weeks no paper has been submitted which could compete for this prize. If the paper in hand should not meet the requirements, the donor has suggested that the prize be transferred and offered for: (a) the determination of the hardness in metals in connection. with super-hardness, (b) in consideration of questions of fuel economy, (c) in consideration of questions of industrial development and labor. J. E. JOHNSON, JR. AWARD This award is made from the income of a fund of $3000 donated by Mrs. Margaret Hilles Johnson in memory of her husband, J. E. Johnson, Jr., who was a prominent engineer, author of two valuable volumes on iron blast-furnace construction and practise, vice-chairman of the Institute's Iron and Steel Committee, and a frequent contributor of papers to the Institute's TRANSACTIONS.

Jan 1, 1925

By W. T. Olsen, R. Ulcer

WHEN a liquid alloy freezes, the solid first formed usually differs widely in chemical composition from that last formed, so that there is segregation in the alloy as cast. For example in the copper-nickel system (fig. 1) the first solid formed from a liquid containing 55 atomic pct Cu may contain as little as 38 pct Cu, while the last must contain well over 55 pct. Three factors may act to decrease segregation from the maximum possible. 1. Diffusion in the cooling solid tends to make the phase homogeneous, decreasing segregation. This may be important at slow rates of cooling. 2. Segregation is impossible without diffusion in the liquid. At extremely rapid rates of cooling there may not be enough time to allow maximum segregation. 3. Supercooling delays nucleation to temperatures well below the liquidus thereby decreasing segregation. Hence the first nucleus in the copper-nickel system may contain well over 38 pct Cu. At sufficient supercooling the first nucleus may form below the solidus, in which case there is no reason to expect any segregation whatever. From these considerations, we could predict that at sufficiently low rates of cooling the alloy would be unsegregated because of factor 1 and at sufficiently high rates of cooling there should also be no segregation because of factors 2 and 3. Considerable segregation should occur only at intermediate rates of cooling. We have demonstrated experimentally that segregation can be completely suppressed by rapid rates of cooling. For the alloys studied, however, these rates are too great to be attained in any commercial practice. An alloy of 55 atomic pct Cu, 45 atomic pct Ni was frozen by cooling at varying rates. The degree of segregation in the solid was determined by X-ray diffraction photographs. Slow rates were obtained by slowly cooling the furnace containing the liquid alloy; fast rates by pouring or ejecting droplets of the alloy into water or iced sodium hydroxide solutions. The cooling rate of the droplets can be cal-culated from their dimensions by assuming reason- able values of thermal conductivity.' The experi-ments were repeated with an alloy of 16.5 pct Cu and 83.5 pct Au. A single experiment also showed a 50 atomic pct Bi-Sb alloy had no segregation at the most rapid quench. The position of back-reflection X-ray diffraction lines is a highly sensitive function of the lattice constant, which in turn depends on the chemical composition of the phase. A phase of varying composition will give broad diffraction lines. By measuring the edges of these lines and making suitable corrections for intrinsic line width, it is possible to determine the range of lattice constants represented. These can be converted to chemical compositions from a lattice constant vs. composition curve. Results are shown in table I. In the copper-nickel system the greatest segregation is found at the slowest cooling rates, where the lowest percentage of copper theoretically possible is found. In the copper-gold system, on the other hand, the degree of segregation is decidedly less at the slowest rates of cooling, being greatest at 11,100°C per sec. At no rate is the theoretically lowest percentage of copper (12 pct) found. At the rates of cooling found in sand and die castings the degree of segregation is large and depends little on the rate of cooling. Acknowledgment Most of the material in this paper is abstracted from a thesis presented by William T. Olsen, Jr. in 1948 in partial fulfillment of the requirements for the degree of Master of Science at the University of California.

Jan 1, 1951