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By John Birkinbine

Secretary's Note.—In printing this paper in the present volume, the figures given in the pamphlet edition have been brought more nearly up to date, the product of 1899 being in many instances inserted. Iron-Ore Resources. In a paper presented to the Institute in 1897,* I discussed the iron-resources of the United States as then developed, calling attention to some principal sources upon which other countries depended. The following statement will give a general idea of the amounts, as compiled from the latest official records, of ores won, and metal produced, in the nations which are important contributors to the world's output. Unfortunately these are not all contemporaneous, since in some countries the statistics do not appear until after one or more years. The statement covers not only pig-iron and iron-ore, but also manganese-ore —the manganese mined being principally used in the production of spiegeleisen or ferro-manganese, and these alloys being generally included in the pig-iron output. Table I, which epitomizes the present situation, shows respectively the countries and the quantities of iron-ore and man-

Jan 1, 1901

By Sidney H. Haughton

WHEN the white pioneers of the eighteenth and nineteenth centuries advanced from the coastal settlements of southern Africa into the interior of the subcontinent, they found it inhabited, more or less sparsely, by brown or black peoples mainly of pastoral habits but equipped with a fighting spirit and certain fighting weapons. Some of the tribes were smiths, others were miners and metallurgists; all used fuel, either industrially or domestically. Some of that fuel was wood, some cattle dung, and in some places the natives mined outcrop coal. Coal was first discovered by Europeans in Natal about 1840. After proper deliberation and after allowing due time for a consideration of all the implications, the Natal Government decided in 1881 (40 years after) to import an English expert to investigate and report on the discovery. Things then moved rapidly, and in what to a geologist is the remarkably short space of eight years, Natal collieries were producing at the rate of nearly 30,000 long tons per annum or 100 long tons per working day!

Jan 1, 1945

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By C. A. Siebert, S. H. Bush

Isothermal temper-embrittlement studies were conducted on a 5140 steel at various temperatures for times as long as 3000 hr. Specimens from the embrittled steel were subjected to impact tests, metallographic examination, microhardness, and lattice-parameter measurements. SEVERAL of the steels in the low alloy group are subject to a pronounced decrease in impact energy if held within, or cooled slowly through, a range of temperatures below the lower critical. This phenomenon, known as temper embrittlement, is quite pronounced in the chromium steels of which AISI 5140 is typical. This study considered the response of one heat of 5140 steel when embrittled isothermally at various temperatures for times as long as 3000 hr. Excellent reviews of the work done in the field of temper embrittlement have been written by Hollomonl and Woodfine.' Both authors list the various theories which have been advanced to explain temper embrittlement. Some of the mechanisms considered were: 1—a transformation below 700°C; 2—an allotropic modification of iron; 3—precipitation from the ferrite of such compounds as carbides, nitrides, phosphides, or chromium oxides; 4—decomposition of retained austenite; 5—modification of special carbides; 6—grain-boundary segregation; and 7—selective distribution of carbides. The present study investigated the changes in hardness, Meyer's number, impact properties, micro-structure, and lattice parameter which occurred on embrittlement. Previous studies considered the influence of microstructure and of prior austenitic grain size3 on the response of 5140 steel to temper embrittlement. Equipment and Procedure All samples were taken from one heat of 5140 steel; the chemical composition of this steel was: 0.43 pct C, 0.86 pct Mn, 0.020 pct P, 0.019 pct S, 0.27 pct Si, 0.84 pct Cr, 0.10 pct Ni, 0.06 pct Mo, 0.10 pct Cu, and the remainder Fe. The material was received as % in. rounds. This stock was cut down to blanks measuring approximately 0.425~0.425~2.196 in. Heat Treatment: The rough blanks were normalized at 1600°F (870°C) for 1 hr, then austenitized at 1600°F (870°C) for 1 1/2 hr, and quenched into an agitated oil bath. The specimens were tempered at 1275°F (690°C) for 5 hr and water quenched. These tempered specimens were designated as the toughened state. Embrittling Treatments: The tempered bars were divided into sets and subjected to the various embrittling treatments listed in Table I. Temperatures from 750" to 1050°F were investigated for times of 1 to 3000 hr. Special tests to determine the effect of heating a short time at a higher temperature after long-time embrittlement at some lower temperature were also conducted. All specimens were water quenched at the end of the embrittling cycle, then ground and notched to obtain standard Charpy V-notch specimens. Impact Tests: The bars were fractured in a 260 ft-lb Charpy impact unit; specimens were fractured at temperatures ranging from —315°F to room temperature. Fixed temperatures used consisted of —315°F with liquid nitrogen, —115°F with dry ice and acetone, and 32°F with ice and water. Intermediate temperatures were obtained by suspending the bars in a jig over the liquid nitrogen, dry ice and acetone, or ice and water.

Jan 1, 1955

By Robert E. Green, T. Hinton

The velocities of the three possible modes of elastic-wave Propagation have been calculated for single-crystal aluminum at 1-deg intervals throughout the standard steveographic triangle. The results are presented as isospeed contours. The deviations between the direction of maximum energy propagation and specirzen axes are presented as arrows drawn within the standard triangle. The orientation factors associated with dislocation nzotion on the primary slip system only and also on all twelve slip systenzs have been calculated for all three elastic waves. The orientation factors associated with a longitudinal standing--7aue resonant specivnen hazle also been calculated. The relevance of these results to ultrasonic attenuation measurements is discussed. DUE to the widespread use of ultrasonics in the investigation of the properties of solids a number of authors15 have discussed in detail the theory of elastic-wave propagation in solids. In this paper the modes of wave propagation are evaluated according to the procedure suggested by reeen' for the case of single-crystal aluminum at 1-deg intervals throughout the standard stereographic triangle. The wave speeds are presented in the form of contour diagrams within the standard triangle. The deviations between the direction of maximum energy propagation and the normals to the wave fronts are presented as arrows drawn within the standard triangle. The orientation-de pendent factors (orientation factors) associated with dislocation damping as derived in the preceding paper6 have been calculated for the case of aluminum at 1-deg intervals throughout the standard triangle. The orientation factors for dislocation motion on the primary slip system only and on all twelve slip systems are presented in the form of contour diagrams, for both the traveling- and the standing-wave conditions. The relevance of these results to ultrasonic attenuation measurements is discussed. ELASTIC-WAVE PROPAGATION Three waves can be propagated in a linear elastic homogeneous anisotropic medium. The velocity of propagation v of each of these waves in a medium of density p can be obtained from the determination of the eigenvalues and eigenvectors of the matrix equa- The A's are a series of moduli which are functions of the elastic constants cij and the direction cosines 1, m, and n of the specimen axis. In the case of cubic single crystals where there are only three nonzero elastic constants cll, c12, and C, the A's are, The solution of Eq. [I] will give the wave speeds (eigenvalues) and the direction cosines a, 0, and y of the particle displacements (eigenvectors). To obtain the direction of maximum energy flux requires the calculation of the energy-flux vector ET with com- w is the angular frequency, A, the amplitude, and v the velocity of the wave. The direction cosines a, b, and c of the energy flux vector are then given by

Jan 1, 1967

By R. H. Kolb

A long term project at Shell Development Co.'s Exploration and Production Research Laboratory has been the improvement of the accuracy and the ease of BHP measurements. As a result of these efforts, two complete and separate systems have now been built for the automatic logging of BHP variations. The first of these is a small-diameter instrument suitable for running through production tubing on a single-conductor well cable. During the development of this instrument, as much emphasis was placed on providing a high degree of usable sensitivity and repeatable accuracy as on obtaining the advantages of surface recording. The second system combines the benefits of automatic, unattended recording with the convenience of a permanently installed Maihak BHP transmitter.' THE CABLE INSTRUMENT For many years the standard instrument for BHP determination has been the wireline-operated Amerada recording pressure gauge or one of several other similar devices. This gauge records on a small clock-driven chart carried within the instrument, and although relatively precise readings from the chart are possible, they are difficult to ob-tain. a Both the maximum recording time and the resolution of the time measurements are limited by chart size, and when a slow clock is required for long tests, the precision of the time measurement is often inadequate. Since it is impossible to determine the data being recorded until the gauge has been returned to the surface, wasted time often results when a test is protracted beyond the necessary time or when it is terminated too soon and must be re-run. Clock stoppage or other malfunctions which would be immediately apparent with surface recording remains undetected with down-hole recording; the test is continued for its full term with a consequent loss in production time. As new uses for subsurface pressure data evolved, the shortcomings of the wireline instrument became increasingly apparent, and the concurrent development of a surface-recording pressure gauge and the associated high-pressure well cable service unit' was undertaken. Description of the Instrument Because of its ready availability and advanced degree of development, the Amerada bourdon-tube element was chosen as the basic pressure-sensing device. This element converts a given pressure into a proportional angular displacement of its output shaft, and a suitable telemetering system was designed to measure accurately the extent of this displacement and to transmit the measurement to the surface and record it. The telemetering system furnishes a digital record printed on paper tape by an adding machine-type printer. The present arrangement provides a resolution of one part in 42,000 over the angular equivalent of full-scale deflection, giving a usable sensitivity of better than 0.0025 per cent of full scale. An additional refinement simultaneously records on the tape the time or the depth of the measurement, also in digital form. When the instrument is placed in operation, an adjustable programer can be set to initiate a read-out cycle automatically at selected time intervals. When subsurface pressures are changing rapidly, readings may be recorded as frequently as once every 10 seconds; when pressures are more nearly stabilized, the period between readings may be extended to as much as 30 minutes. Because the instrument is surface-powered as well as surface-recording, the maximum period of continuous logging is (for all prac. tical purposes) unlimited. The subsurface instrument is a tubular tool, 1 1/4-in. in diameter and 6.5 ft in length, operating on 12,000 ft of conventional 3/16-in. IHO logging cable. The transmitting section, mounted above the bourdon-tube element in place of the regular recording mechanism, contains no fragile vacuum tubes or temperature-sensitive transistors. This unit has been laboratory-tested to 1 0,000 psi and 300°F and has performed dependably during a number of field operations. The down-hole transmitting arrangement can be fitted to any standard Amerada pressure element, regardless of range and with no modification of the element itself. Calibration To obtain a repeatability commensurate with the sensitivity and resolution of the instrument, it was necessary to develop a special calibrating technique. The manufacturers of the Amerada recording pressure gauge claim an accuracy of only 0.25 per cent of full scale, which is a realistic figure for normal calibrating and operating procedures. An exhaustive investigation was made of the errors inherent in the bourdon-tube element, itself, independent

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

L. S. Austin, Denver, Colo. (communication to the Secretary) : Mr Hartman says (p. 4 of the pamphlet) that the penetration of air into the crucible of the blast-furnace " is, of course, a function of the diameter of the nozzle." To this I would emphatically take exception. Fig. 1 represents a vertical ideal section of tuyere, cruciblewalls and charge, immediately at the tuyere, in which the currents of air are represented, both in quantity and in direction, by the tortuous black-lines emanating from the nozzle-opening and passing through channels of the least resistance. As an electric current, flowing by various conductors to a common point, is carried in quantity inversely as the resistance of those conductors, so here the air ramifies through the most open cavities or channels, relatively little of it passing where the resistance due to fine materials is great. This figure represents the course of currents in the vertical plane only. As a matter of fact, they pass away in every plane, as opportunity offers. The effect of blocking or decreasing the area of the nozzleopening would certainly only decrease the quantity of air entering by that particular tuyere, without assisting penetration. The large channels (b, b, Fig. 1, for example) would still carry the larger part of the air, while again the smaller channels (a, a, a) would continue small and take no larger percentage of the air than before. These channels momentarily change, however, with the slow descent of the coke. Further on (p. 5), Mr. Hartman describes the dispersive effect of a single lump of fuel. He has only to conceive the entire spaces before the tuyere-nozzles as filled with such lumps, in order to parallel the condition of affairs I have just explained. It is where the large pieces of the charge come down, that the mass is the most open, and the blast passes most freely. On the other hand, wherever the fine ore collects combustion proceeds slowly, because of the smaller supply of air. The

Jan 1, 1899

By John Richards

MY remarks will be confined to the experience of our company in mining the No. 8 seam of coal in Ohio, although I believe that the relationship existing here between the method of mining and the method of cleaning will hold true in many of the coal seams throughout the country. The increasing demand for a cleaner and better graded product is being felt throughout the entire coal industry, and the methods of mining are playing an important part in the control of various sizes and quality of coal produced. We have found a definite relation between the mechanical loading of coal and its preparation for the market. In the No. 8 coal seam the location of the non-combustible material is regular. The' marketable coal lies in three benches, separated by streaks or bands of impurities. These impurities must be removed from the coal to properly pre pare the product for the market. Where hand-loading methods are employed, the loader removes as much of this non-combustible material as possible at the working face. The impurities that are missed by the loaders are removed as the coal passes through the preparation plant, by means of picking tables. As this method of cleaning cannot improve the quality of the extremely fine sizes, a practice has been established in the company's hand-loading mines, of undercutting the coal about 2 in. above the bottom of the seam, thereby eliminating any possibility of impurities caused by the cutting machines cutting into the rock bottom below the coal seam.

Jan 1, 1934

By Francois Clerf

IRON ORE fields are situated in both the East and West of France (see maps). The eastern deposit is by far the most important from a tonnage point of view, not only in France, but in all Europe. The ores of this region are known as minette, and are situated in the Lorraine ore fields and the Briey plateau. The iron ores of the West are those of Normandy, Anjou and Brittany. Before the war, a large number of important German companies had acquired considerable interests in these western fields and a heavy trade with Westphalia had begun. Recently, however, conditions have changed and some of the mines of Brittany and Anjou are now idle. From a geological point of view, in Anjou and Brittany, a series of synclines extends from the northwest to the southeast, containing a number of seams of varying thickness and generally intercalated in Silurian and sometimes in Devonian formations. The ore is generally a hematite or a magnetite. The composition varies from 48 to 52 per cent of iron and from 8 to 12 per cent of silica. Con¬servative estimates indicate a con¬siderable tonnage of workable ores (150,000,000 metric tons).

Jan 1, 1936

By J. C. Bowling

The services provided by consulting engineers to the mineral process industry are briefly described. The organization of a multi-discipline consulting firm is outlined. Finally, the role of a consulting engineering firm is amplified by a description of its activities in the design and construction of a mineral process plant from inception to start-up.

Jan 1, 1978

By Heinrich Freyn

THE American iron and steel manufacturer finds himself to-clay barely at the threshold of enormous possibilities for practicing rational economy in the use of fuels. The fuel cost is by no means the smallest of items which enter into the cost of manufacture of iron and steel products, but the great wealth of this country in high-grade fuels, together with a protective tariff, has heretofore made fuel economy relatively unimportant. In Germany, the use of raw coal for the purposes of iron and steel manufacture has been all but abandoned and large sums of money, formerly irrevocably wasted, are now being saved. When scanning the literature of this country devoted to the application of gas power, but little information will be found on a subject which, however, is destined to become of considerable importance in the United States, namely, the use of coke-oven gas for the generation of power in gas engines. This lack of information can be traced to the fact that the regenerative by-product coke oven with its large amount of surplus gas is still far from having attained in this country the universal application which it has found in Europe. This statement needs hardy any corroboration other than the evidence of statistical investigations made by E. W. Parker of the United States Geological Survey, according to which only approximately 25 per cent. of the total coke produced in this country in 1912 was made in by-product coke ovens, whereas 75 per cent. was produced in bee-hive ovens. This entailed the enormous loss of over $80,000,000 in non-recovered by-products, such as gas, tar, and ammonia, without considering the substantial loss due to the non-recovery of benzol from the coal. There are two more or less distinct fields of application of the by-product coke oven: one, to furnish as the main product metallurgical coke of specified quality, and surplus coke-oven gas as the by-product, and the other, to carbonize high-volatile coals, and thus produce as the main product large quantities of gas, high in heat value and rich in illuminants, adapted primarily for domestic heating and lighting, while domestic coke becomes the by-product.

Jan 4, 1914

By W. E. Wrather

DURING the war the mineral industry, and metal mining in particular, extended itself more than any other to attain the limit of its productive capacity. Likewise, probably no other industry went quite so far toward jeop¬ardizing its own economic future through depletion of material reserves. Once we looked to Europe for most of the manufactured goods we needed. Our own limited mineral requirements were easily supplied from mines near the Eastern seaboard. With expansion and industrialization, our mineral needs increased in proportion, and the centers of mining activity moved westward to Michigan, Wisconsin, Minnesota, and the Tri-State district, where seemingly inexhaustible high-grade deposits of iron, copper, lead, and zinc ores were opened and rapidly developed.

Jan 1, 1946

By Kandalla Ravindranath, C. C. Patel

Studies of the adsorption of dialkyldithiocarbamates at the surfaces of galena and sphalerite have shown that characteristic contact angles are obtained at galena surfaces in the 7-10 pH range, whereas lower angles are obtained at unactivated sphalerite surfaces even at pH 71 Further, the angles at sphalerite surfaces progressively decrease with increase in pH. However, when sphalerite is activated with cupric sulfate, characteristic contact angles are obtained at pH 7 and beyond. This shows that galena and sphalerite can be selectively floated with dithiocarbamate collectors at pH 7 and beyond. Experimental Materials Ore: The lead-zinc ore for the present study was obtained through the courtesy of the Geological Survey of India from Dariba, Udaipur, Rajasthan, India. The average ore analyzed 15.5% lead, 11.6% zinc, 6.7% iron, 15.6% sulfur and 36.6% acid insolubles. The ore was crushed in a Denver laboratory rod mill and sieved in a Denver automatic sieve shaker to obtain a -200- to +250-mesh (Tyler standard) fraction. This particular size was chosen because it was conducive to good liberation of sulfide minerals, both from one another and from gangue minerals. Collectors: Dimethyl, diethyl, diisopropyl and diisobutyl dithiocarbamates were prepared and purified by the methods described by Klopping and Van der Kerk.2 A freshly prepared 0.03% dithiocarbamate solution in distilled water was used for flotation studies. Frother: A 0.03% solution of pine oil in ethyl alcohol was employed. Activator: 7.3 g of cupric sulfate pentahydrate were dissolved in 1 1 of water and used for the activation of sphalerite. Depressant: 16.0 g of zinc sulfate heptahydrate were dissolved in 1 1 of water and used for the depression of sphalerite.

Jan 1, 1972

By Klaus Schwerdtfeger

The rate of formation of silicon monoxide from silica spheres has been measured at 1500°C in H2, H2-H2O, H2-He, H2-Ar, and CO-CO2 gas mixtures. Indications are that in the hydrogen-containing gases the reaction rate is mainly determined by convective diffz~sion. In the CO-CO2 mixtures the rate approches a constant value which is independent of sphere diometer (and gas velocity). This suggests that a surface reaction becomes rate controlling in CO-CO2 gas. WHENEVER silica is exposed at elevated temperature to a strongly reducing atmosphere there occurs, inevitably, a volatilization of silica by the formation of gaseous silicon monoxide. Because of the importance of this reaction in metallurgical processes and laboratory experiments, its kinetics were studied in the present work. EXPERIMENTAL The spheres made of vitreous silica were suspended by a molybdenum wire in the hot zone of a gas-tight high-purity recrystallized alumina furnace tube of 3.1 cm internal diam and 100 cm length. Molybdenum wire resistance heating was used. A purified H2, H2-H2O, H2-He, H2-Ar, or CO-CO2 gas mixture was passed through the tube, from top to bottom. The amount of silicon monoxide formed was determined by weighing the silica balls before and after the experiments. The silica balls were made from commercially available translucent fused quartz glass. In experiments with hydrogen-containing gases the silica stayed vitreous during the experiment, whereas in experiments with CO-CO2 mixtures, which were performed over longer times, the balls were always crystallized to cristobalite (as determined by X-ray examination) at the surface. Constant-pressure head capillary flowmeters were used to control the composition of H2-He, H2-Ar, and CO-CO2 gas mixtures. The oxygen and water vapor were removed from the gases containing hydrogen by passage through columns containing platinized asbestos (450°C) and an-hydrone. The CO was purified from O2 and CO2 by passing it through activated copper (200°C) and through ascarite. The H2-H2O gas mixtures were prepared by passing purified Hz through a mixture of oxalic acid dihydrate and anhydrous oxalic acid held at a constant temperature in a water bath. The equilibrium water vapor pressures of oxalic acid dihydrate-anhydrous oxalic acid mixtures were taken from the available data.1 The furnace system was checked for sufficient gas tightness at regular intervals. As an additional check, the H2O and CO2 contents were measured in the exit gas and were found to agree closely with the metered contents when H2-H2O or CO-CO2 mixtures were used. When purified H2 was used, H2O pressures found in the exit gas were always below 0.1 mm Hg. These contents originate either from an incomplete reoxidation of silicon monoxide in the cold part of the furnace or from small leaks which cannot be avoided. If the latter is the case, such small uncontrolled H2O contents decrease the partial pressure of SiO in equilibrium with SiO2 by less than about 7 pct, which is considered small in comparison to other experimental uncertainties. The temperature of the furnace was controlled automatically in the usual manner. The reported temperature was measured with a Pl-Pt/l0pct Rh thermocouple and was accurate to ± 5°C. TRANSPORT-CONTROL LED RATE OF REDUCTION The gaseous convective diffusion from the surface of a sphere can be predicted from the semiempirical relationship obtained by Ranz and Marshall2 in a study of the evaporation of water and benzene drops in air. The following equation applies:

Jan 1, 1967

By AIME AIME

CHARACTERIZING the annual meeting as the biggest and best one yet has happened so repeatedly that some may suspect it has become a conventional phrase, like "good morning," and yet, what else can be said when not only one but all the many who express an, opinion use exactly those words, while the first of the two adjectives refers to a physical fact that is established by count. Perhaps there were hose who thought it not the best, but if so they were too tactful to say it out loud. So without further ado . let us admit that the one hundred and thirty-ninth general meeting of the A. I. M. E. held; as our By-laws provide, in New York during the third week of February, was the biggest and best of them all. Perhaps it is because we appreciate friendliness more as we grow older, but somehow the friendly atmosphere seems to rise slowly in temperature with the passing of the years. The actual atmosphere on the opening morning was quite the contrary, Feb. 17 being the coldest clay, so far, of this winter, and the suburbanites claimed that their thermometers had registered 5" below zero when they got up, though the official records of the weather man did not go that low. From that time the temperature steadily rose until Thursday afternoon, when the official record of 66" constituted a record high for Feb. 20 at New York. The weather man explained it by learned discussion of highs and lows, but we suspect the A.I. M. E. members must have had something to do with it.

Jan 1, 1930

By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By Kirtley F. Mather

FROM almost every point of view, petroleum was "strategic mineral number one" during the World War that ended in 1945. Even the spectacular advent of the atomic bomb in the final days of the conflict did not displace it from its position of prime importance, although within a few years uranium will almost certainly be the "number one" material in the minds of military strategists, if it is not even now in that position. But both as fuel and as raw material for chemical industries, petroleum will hold the center of the stage for many years to come. Hardly any other substance illustrates so fully the manner in which science and technology may be combined to achieve the utmost success in contributing to human efficiency and comfort. Fundamental to any understanding of the problems implied by my topic

Jan 1, 1948

By John M. Bostwick

Bitumen is a general term for a group of materials composed of mixtures of hydrocarbons that are fusible and soluble in carbon disulfide. Included in the group are petroleum, asphalts, asphaltites, and mineral waxes. Asphalt is a dark-colored, cementitious solid or semisolid, which generally softens on heating and resumes a more viscous or solid state when cooled (personal communication). It is found in native form in fissures and pore spaces in rocks and as lakes. It is also obtained from the residues produced in petroleum refining. Asphaltites are black, naturally occurring solid bitumens. They are generally shiny and break with a conchoidal fracture. Common asphaltites are gilsonite (uintahite), grahamite, and glance pitch. Mineral waxes are solid or semisolid, relatively nonvolatile bitumens of various colors, having an unctuous feel and waxy luster. Of the native waxes, ozokerite is the best known. Montan wax is also classed as a natural wax, although it never occurs in the pure state and must be extracted from lignite or cannel coal (Ladoo, 1920). Mineral waxes may also be obtained by pyroprocessing of petroleum, lignite, and peat. Pyrobitumens are dark-colored, solid hydro- carbons that are infusible and relatively insoluble in carbon disulfide. They are so-called because they will yield liquid and gaseous hydrocarbons only when heated. Asphaltic pyrobitumens are defined as "substantially free of oxygenated bodies" and include wurtzilite (elaterite), albertite, and impsonite (Thrush, 1968). Nonasphaltic pyrobitumens contain oxygenated bodies; examples are coal and peat. The nonasphaltic type will not be discussed further. Petroleum Asphalts Asphalts refined from crude petroleum have almost completely replaced the native types. Refineries can produce asphalts in every desirable grade more economically and in greater quantity than the native types and with a variety of properties that meet the requirements of the various manufacturers using them. For all practical purposes, it is estimated that more than 95% of the asphalts consumed in the United States are refined from crude petroleum (private communication).

Jan 1, 1975