Search Documents

By R. T. O’Brien, J. M. W. Mackenzie

A microelectrophoresis technique has been used to measure the zeta potential of quartz over a range of pH and Ni (11) and Co (Ilj concentrations. Results have been discussed in terms of adsorption of Ni (11) and Co (11) cations and hydroxide precipitates. Possible relationships between the experimental results and the formation of lateritic nickel deposits have been discussed. The adsorption of metallic cations to the surface of silicate minerals is of significance in many industrial and natural processes. In an earlier publication,' the adsorption of Fe (111) to the quartz surface, a phenomenon of importance in flotation, was studied qualitatively using microelectrophoresis techniques. This paper reports the extension of this work to an investigation of the adsorption from aqueous solution of Co (11) and Ni (11) to the quartz surface. The adsorption of these metals was of interest for two reasons; firstly, the importance of such an adsorption process in the formation of nickel deposits by the lateritization of nickeliferous rocks, and secondly, the comparison of electrophoresis data for these metals, whose hydroxides precipitate in the pH range 7-8, with similar data for Fe (111) where the hydroxide first precipitates at pH 2.8. The development of laterites is essentially a near-surface geological process involving vertical and, in part, horizontal redistribution of elements derived from rock-forming minerals. This redistribution of elements leads to the formation of layers within the lateritic profile which are enriched in one or more of these elements and, depending on the nature of the original rocks, continued lateritization may give rise to iron ores, bauxites or nickeliferous laterites. The mechanisms discussed in this paper deal with the last mentioned type of deposit although the considered factors are applicable to laterites in general. Nickeliferous laterites are derived from basic and ultrabasic rocks containing ferro-magnesian silicates. These rocks may be partly or wholly converted to serpentinites. Besides their high Mg, Si and Fe contents, they also contain small amounts of Mn, Al, Cr, Ni, Co, Cu and Zn. The nickel content is usually near to 0.2-0.3%, but for economic use this must be increased during lateritization to over 1% and preferably over 2%. The zone of nickel enrichment is usually at some depth within the lateritic profile. Unpublished work by Mr. O'Brien on nickel-bearing laterites in eastern Australia indicated four visually different types of material which were separated from crushed samples under a stereo-microscope. Although chemical analyses indicated that all four types of fragments contained 2-4% nickel and smaller amounts of cobalt, X-ray diffraction and optical studies revealed only quartz, hematite and chromite as well as, in one of the types, a serpentine mineral. No distinct, nickeliferous minerals were detected. Furthermore, it was possible to extract some 60% of the nickel content of the laterites with cold 0.5N hydrochloric acid. It was therefore postulated that much of the contained nickel was present as amorphous, adsorbed material. In considering this fact, as well as the problem of the actual method of transfer and fixation of elements within the lateritic profile, it was further postulated that the transfer of these elements probably took place partly as solutions and partly as colloids and that the fixation of these was caused by adsorption and flocculation. The existence of nickel in solution in water draining from serpentinites has been confirmed by Smurov.2 Although we have no evidence for the transportation of nickel in the colloidal state, it is well accepted that colloids are important in the formation of laterites. Previous work by Mr. Mackenzie' has already indicated that iron may be adsorbed on quartz under conditions which could be expected in a lateritic profile, but no information was available for nickel or cobalt. Although adsorption possibly also takes place on minerals other than quartz, the latter is significant because silica is an important constituent of the silicate parent rocks. During lateritization, it is released to form free quartz and it is likely that it is initially extremely fine-grained. This would provide abundant opportunities for adsorption and it was de-

Jan 1, 1970

By G. F. Comstock

A serious disagreement as to the effect of titanium on the hardenability of steel exists in published references to this subject. Kramer, Hafner and Toleman reported' that acid-soluble titanium decreased creased the hardenability, with multiplying factors less than unity according to [ ] Grossmann's system for calculating hardenability from the composition. Crafts and Lamont, on the other hand, showed2 how titanium increased the hardenability, with multiplying factors up to nearly 1.7 for about o.' per cent titanium, though reducing the hardenability with higher titanium. Their data, however, were obtained almost exclusively from steels containing more than 2.4 per cent manganese, and thus should be considered as applying mainly to manganese steels. Likewise, the results of Kramer, Hafner and, Toleman regarding titanium are subject to the limitation that although they eliminated the effect of the insoluble titanium compounds from their calculations, they did not make a similar correction for the carbon that was combined with titanium and therefore occurred in a similarly ineffective form. It is suggested by the literature referred to that titanium may have different effects on hardenability, depending on the mode of its occurrence in the steel. The different effects on strength, ductility, etc., have already been discussed by the author.3 In the present discussion some comparisons, on the basis of hardenability as revealed by the Jominy end-quench test, are given between three titanium and two non titanium steels heat-treated in the same ways, and between other titanium steels heat-treated in several different ways. COMPARISON OF PLAIN-CARBON, VANADIUM AND TITANIUM STEELS The five steels used for these experiments were commercially melted and rolled products received in the form of 1.5-in. rounds from three different mills. Their analyses are given in Table I. Steels 2, 3, and 4 are from the same basic electric heat, containing 0.009 per cent of phosphorus and the same amount of sulphur. They were made by, adding aluminum and low-carbon ferrotitanium to different ingots. No. I is a plain-carbon coarse-grained S.A.E. 1040 steel made by the basic open-hearth -process. No. 5

Jan 1, 1945

By Joseph Pogue

IN 1920, 531 million barrels of crude petroleum were consumed in the United States. As imposing as this figure is, the fact that the domestic consumption of crude petroleum has increased at an average rate of 10 per cent. a year for the past decade is more striking. Will this rate of increase in demand continue? If so, the year 1930 will call for 1260 million barrels of petroleum-a staggering volume. On the other hand, may we expect the demand for petroleum to grow as rapidly as it did when the automotive industry was having its most phenomenal expansion? If not, to what extent will the growth of oil requirements decrease? When and to what degree will the petroleum industry become affected by the economic law of diminishing returns? Obviously, this matter requires careful analysis, especially as both national and industrial planning must be predicated upon present estimates of the requirements of the future. The purpose of this paper, accordingly, is to project, as closely as present limitations of knowledge permit, the course of the demand for petroleum in the United States over the next ten years. At first, the problem of estimating the future of a demand as complex as that for petroleum might appear insoluble. Fortunately, however, there are several scientific methods of approaching the problem, centering around a study of rates of industrial growth, which lend considerable hope that the requirements of the immediate future in this field may be approximated with sufficient closeness to have practical value as a basis of action.

Jan 3, 1922

By H. L. Eiselstein, F. P. Huston, B. B. Betty

An extensive program for the establishment of creep data on high-nickel alloys has been in progress during the past seven years. This paper presents the accumulated data on two solid solution alloys, cold-drawn, annealed Monel and cold-drawn, annealed Inconel. Data on these two alloys in other conditions will be published at a later date. Monel, a nickel-copper alloy, is normally considered a corrosion-resistant material, but it will be shown that it also has considerable creep strength, validating its use at temperatures up to and including 900°F. Inconel, a nickel-chromium-iron alloy, is definitely a heat-resisting alloy possessing good creep strength and oxidation resistance up to iiooOF., and because of its oxidization resistance has been used successfully at much higher temperatures for lightly stressed parts. The literature contains but meager data on the creep properties of high-nickel alloys. Howevcr, Bennett and McAdam have presented a substantial quantity of creep data for cold-drawn Monel.1 The material as tested was not representative of mill production for it was cold-drawn to a reduction of area of 40 per cent as against 13 per cent, which is the mill standard for Monel. Twenty-two individual tests were run on each alloy in the investigation described in the following pages. The data and curves presented herein represent an integration of all the tests to obtain the most accurate picture of the creep properties of these alloys. Neither of the two alloys was found to be embrittled by the combination of temperature and stress, as evaluated by room-temperature tensile and impact tests that were made following creep testing. These data indicate that no tendency toward embrittlement exists. It is recommended that 6300 lb. per sq. in. be used as a working stress for cold-drawn, annealed Monel at 900°F. and 13,200 lb. per sq. in. for cold-drawn, annealed Inconel at the same temperature. Table 8 lists recommended working stresses, based on 80 per cent of the stress to produce a minimum creep rate of 0.01 per cent per 1000 hr., for Monel and some steels. Equipment The equipment used for these tests consists of Colville creep-testing machines manufactured by the Tinius Olsen Testing Machine Co. The load is adjusted, depending on the stress level, to give an error in the stress of not more than ± 0.1 per cent. This is based on considerations of lever sensitivity and the stress used for the standard (A.S.T.M. Tentative Standard E22-38T) 0.505-in. diameter creep specimen having a 2-in. gauge length. The single-specimen furnaces are provided with primary and secondary windings, from

Jan 1, 1945

By W. Rostoker, R. F. Domagala, R. P. Elliott

The phase equilibria of the Hg-Th system over the composition range 0-100 pct Th and temperatures up to 1000°C have been studied for a small-volume, closed system. The solubility of Th in liquid Hg is about 5 pct at 300°C and decreases sharply with decreasing temperature. Two intermediate phases occur, Hg3 Th and HgTh. The structures of these are hexagonal (nonideally close-packed) and face-centered cubic, respectively. The HgTh phase decomposes eutectoidally at 400°-500°C. The solubility of Hg in solid thorium seems to be negligible. AFULL-phase diagram for this system would have to be defined on temperature-composition-pressure co-ordinates. This paper describes the pseudo phase diagram of a closed system, that is, where the alloy enclosed in a small volume equilibrates with a vapor pressure of mercury dictated by composition and temperature. Because of the experimental difficulties in studying a system of this nature, many of the phase relations can only be sketched. Alloy Preparation Alloys over the full range of composition were made from triple distilled mercury and one of two grades of thorium. For the bulk of the work, a calcium-reduced metal in sintered pellet form of reported 99+ pct total thorium content was used. Arc-melted specimens of this thorium gave a hardness of 135 VPN. The microstructure showed small primary dendrites of ThO2. A number of alloy compositions were made with a high-purity, iodide-decomposition thorium metal. The are-melted hardness of a button of this material was 35 VPN. Although the microstructure of the arc-melted specimens showed no dendrites of ThO2, there was definite evidence of an unidentified phase enveloping the grain bound-aries. There were no distinguishable differences between the constitution of alloys made with the two grades of thorium metal. Under normal conditions thorium is not wetted by liquid mercury. The film of ThO2 on all thorium metal cannot be penetrated by either liquid or vaporous mercury. It was therefore necessary to comminute thorium in the presence of mercury under such conditions that oxide films could not reform on the newly exposed metal surfaces. This was accomplished by the use of a high-speed, carbide-tipped rotary cutter incorporated in a chamber purged with argon and connected at the bottom to a demountable Vycor bulb containing a weighed amount of mercury. This experimental device is fully described in a separate paper.1 Alloy compositions were calculated by weighing the empty bulb, the bulb containing the mercury, and the bulb containing the mercury and the thorium chips. Many alloys were analyzed chemically for thorium and/or mercury after subsequent homogenization; the agreement between analyzed and calculated compositions was invariably very close. Bulbs containing the requisite amounts of mercury and fine thorium chips were clamped off, removed to a sealing unit, evacuated and sealed. Amalgamation under these conditions proceeded rapidly even at room temperature. To insure homogeneity, the specimens were annealed to 300-400°C. Alloys containing less than 30 pct Th remained pasty after all treatments, indicating an equilibrium condition of liquid plus solid. Alloys with more than 30 pct Th were transformed into a dark powdery product. These latter specimens were annealed for times of up to 1 week to complete interdiffusion. Many of the alloy compositions are pyrophoric. On exposure to air they oxidize with considerable evolution of heat to a mixture of ThO2 and free mercury. It was mandatory that alloy specimens be handled in a "dry box" purged thoroughly with argon. All X-ray diffraction specimens were powdered, screened, and sealed in capillary tubes within the dry box. Experimental Procedures Thermal analysis experiments, useful only in the mercury-rich region of the system, were conducted with the alloys in their original containers. A reentrant thermocouple well formed an integral part of the bulb. These bulbs were heated in a silicone oil bath and cooled in a dry ice-acetone mixture. The rates of heating and cooling were slowed by immersing the specimen bulb in a larger tube containing silicone oil. This provided a suitable thermal lag. In all tests, pure mercury was run as a basic standard. While the invariant reaction at about the melting point of mercury was detected by thermal analysis, the heat effect at the liquidus was not sufficient to produce an inflection in the cooling curve. It was necessary to determine the liquidus temperatures at the mercury-rich end of the system by "breaks" in electrical reslstivity versus temperature curves for individual alloys. The apparatus for this purpose consisted of a pyrex tube about 2 in. diam and 12 in

Jan 1, 1959

By John W. Brauns, David H. Orr

9.1-1. Description and Basic Function. A conventional railroad haulage system for a surface mine performs the function of transporting the ore and/or waste out of the pit to a crushing plant or dump. Trains consisting of a locomotive and gondola or side-dump care suitable for loading by power shovels are used. Gondola cars are restricted to hauling ore as a rotary dumper is required to unload them. Side-dump cars are more versa- tile, being satisfactory for carrying both ore and waste; but because of their additional dumping mechanism they are likely to be more expensive to maintain (12). Also they weigh up to two times as much as a flat-bottom car of the same capacity, and, therefore, fewer cars can be hauled per train. Standard-gauge track is most commonly used. Track systems incorporate temporary track of low quality in areas where moves are frequent and permanent track of high quality on main lines. Rail haulage enabled open pit mining to establish its reputation, for efficiency. Prior to World War II it was the principal type of transportation used in large pits. Other successful surface mine haulage methods have been developed since that time. These have served to supplement railroad transportation, permitting selection of a method that is best adapted to the peculiar requirements of each mining project. 9.1-2. General Applicability and Controlling Physical Conditions. For handling rough rock, the shovel-train system is unexcelled (6). The ideal application is in a physically large, but not excessively deep, open pit mine from which the coarsely blasted ore and waste must be transported distances in excess of three miles. If, in addition, a high production rate is to be maintained, railroad haulage will probably afford a lower cost per ton transported than will any other haulage method. Relatively gentle

Jan 1, 1968

By Charles Smeal, Robert J. Schafer, Max Quantinetz

Normally metal powders cannot be ground to sub-micron sizes because of welding and agglomeration phenomena. Through the use of selected grinding aids and grinding fluids, nickel and other metal powders have been ball-milled as fine as 0.1 It was found that certain inorganic salts are more effective grinding aids for metal powders than conventionally used surfactants. METAL and alloy powders are used to produce reagents, pigments, coatings, solders, brazes, and parts for industry by powder metallurgy techniques. They are also combined with refractory compounds to produce cermets and dispersion-hardened products. One of the interests at the Lewis Research Center has been to explore the potentialities of the dispersion strengthening process. Since the work of Ir-mann, many investigators have shown that the strength of dispersion-hardened products may increase with decreasing interparticle spacing.24 One approach to achieving small interparticle spacing is to combine fine refractory compounds and metal powders, preferably below 1 in size. In attempting to obtain fine metal powders, it was found that until very recently the best that could be obtained from commercial suppliers, particularly of ductile metals, was about 1.0 . Interest was therefore developed in providing finer metal powders for dispersion-hardening studies. Information obtained from the literature, from others working in the field, and from prior experimental work performed at NASA, led to a consideration of ball-milling as a technique to produce the desired materials. Some of the variables associated with ball-milling are the size, material, and nature of construction of the grinding container; the nature and amount of the grinding material and material to be ground; and the nature and amount of the grinding liquid and grinding aid, if employed, and the grinding time. In all ball-milling, welding and agglomeration can oc- cur as well as grinding. Because of the tendency of ductile metals to weld together, they are difficult to grind.5 The ultimate particle size obtained on grinding is generally the one at which the rate of grinding becomes equal to the rate of welding. To help delay welding and thus obtain smaller particle sizes, grinding aids are often employed. The principal objective of this investigation was to produce submicron metal powders by ball-milling the powders with selected grinding aids and grinding fluids. A secondary objective has been to attempt to explain the variations observed in grinding behavior by considering possible grinding mechanisms and correlating various parameters with grinding effectiveness. Three groups of ball-milling experiments were run; one in which the grinding aid was varied, a second in which the grinding fluid was varied, and a third in which the material being ground was varied MATERIALS, APPARATUS, AND PROCEDURE In the first group of experiments in which the grinding aid was varied Inco Carbonyl Grade B nickel powder initially 2.5 (all sizes refer to average particle size as measured by Fisher Sub -sieve Sizer) was used as the material being ground and 200-proof ethyl-alcohol as the grinding fluid. Surfactants, representative of typical organic structures, were selected as grinding aids. Inorganic salts used as grinding aids were chosen on the basis of the size and valence of their ions. Water soluble salts were used in order to facilitate their removal from the slurry after grinding. In the second set of experiments, grinding of the 2.5- Ni powder was tried in four different grinding liquids; water, cyclohexane, n -heptane, and methy-lene chloride. In this study seven grinding aids selected from those tried in the first group of experiments were employed. In the third group of experiments 200-proof ethyl alcohol was again used as the grinding fluid to mill Cu, Cr, Fe, Ag, and Ni powders of various initial particle sizes' All mill charges contained 300 ml of grinding liquid and 3000 g of 1/2 in. stainless steel balls. When inorganic salts were used as the grinding aid, 70 g of salt and 210 g of metal powder were employed, and with surfactants 6 g of grinding aid and 300 g of

Jan 1, 1962

By A. K. Mukherjee, John E. Dorn

The effects of strain rate and temperature on the critical resolved shear stress for (321)[111] slip were determined for the silver-rich CsCl type of intermetallic compound AgMg. The flow stress increased only slightly as the test temperature was first decreased below room temperature; a rapid increase in the flow stress was obtained with yet further decrease in temperature from about 250' to 4OK. The effect of both the temperature and strain rate on the flow stress over the low-temperature range could be rationalized satisfactorily in terms of the Peiwls mechanism when the deformation was controlled by rate of nucleation of pairs of kinks. IN spite of the well-documented interest of metallurgists and engineers concerning the mechanical behavior of intermediate phases and intermetallic compounds, very little definitive information is available on this important subject. As recently summarized by westbrook,1 only limited and modest progress has been made thus far in elucidating the details of the mechanism of plastic deformation for the intermetallic compounds; the available information largely concerns phenom-enological descriptions of empirical observations and experimental facts, principally with reference to poly crystalline aggregates. The present report on the elucidation of the rate-controlling mechanism for slip in the bcc structure of AgMg is part of the comprehensive program of a systematic investigation on the mechanical behavior of intermetallic compounds. The intermetallic compound AgMg has a CsCl type of lattice structureZ and is completely ordered up to its melting point of 820c3 This material was selected for our present investigation because of its simple crystal structure, moderate and congruent melting point, ordered structure persisting up to the melting point, and some solubilities of the constituent elements, which could be expected to help in the growing of single-crystal specimens. Whereas previous investigations on the properties of AgMg include hardness,*"6 slip systems,7 tensile flow stress of polycrystalline specimens,' and electrical resistivity,4 the current investigation will be directed principally at elucidating the rate-controlling dislocation mechanism responsible for slip in single crystals at low temperatures. It will be shown that the strain rate is consistent with a model involving the rate of nucleation of pairs of kinks by the Peierls mechanism for plastic deformation. EXPERIMENTAL TECHNIQUES Single-crystal specimens of the AgMg intermetallic compound were prepared and tested as follows: 1) A master alloy ingot of AgMg was produced by melting and chill casting the high-purity silver (99.995 wt pct) and high-purity magnesium (99.997 wt pct) in an induction furnace under a helium atmosphere. 2) Sections of the above-mentioned ingot were placed in a graphite mold containing a spherical cavity in which a single-crystal sphere of 1 in. diam was grown under helium by the Bridgman technique. 3) The operative slip systems were investigated at room temperature on a singlecrystal of AgMg, from measurements of the angles made by the slip traces on the two surfaces of the specimen, which were at 90 deg to each other. The investigation confirmed that the AgMg compound undergoes slip primarily in the (321) plane and in the [Ill] direction, but a small amount of secondary slip was also noticed in the (112) (111) system. No slip was observed in the (110) planes. 4) The single-crystal sphere, mentioned earlier, was oriented in a graphite mold containing a cylindrical cavity of 3/8 in. diam above the spherical receptable to give the angle xo = 45 deg between the axis of the cylindrical bar and the normal to the slip plane (321), and the angle AO = 45 deg between the slip direction [Ill] and the axis of the bar. Oriented single-crystal bar seeds were produced by melting, under a helium atmosphere, a polycrystalline bar in the cylindrical cavity above the oriented spherical seed and by growing an oriented single-crystal bar from the seed. 5) Finally, oriented single-crystal specimens were grown from these cylindrical seeds. 6) The cylindrical specimens were machined in a High-Tension Spark Cutting unit to give a 2-in. gage length. The spark-machined gage section was elec-tropolished in a bath containing 200 ml of H3PO4,

Jan 1, 1964

By Gerhard Derge

THE chemical and physical properties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use, These processes are carried out at high temperatures and involve such complex chemical systems that fundamental scientific knowledge of the properties and behavior of these slags is inadequate. Various hypotheses have been proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenck1 and the recent papers of Chipman and co-authors.2-5 Another proposal is that these compounds dissociate by completes or partial ionization, the evidence for which has been reviewed by Martin and Derge.7 Whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: I, Studies of solidified slag samples by X-ray diffraction, petrography, and similar methods that can be used at room temperature, The correlation of this information with the high-temperature properties of the molten slag is uncertain, 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature, However, even these data present problems of interpretation because they require a complete knowledge of the metal phase, 3, Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret, Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information, The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems CaO-SiO2 and CaO-A1203-Si02 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1946

By J. B. Austin

In considering so complex a process as the smelting of iron in the blast furnace, there is obviously no single method of calculating efficiency that gives a complete appraisal of the performance of the furnace in all its several functions; such a comprehensive view as is required to evaluate producing ability and manufacturing costs for a given furnace is obtained only by considering a group of efficiencies, each of which measures the performance of the furnace from a specific point of view. For instance, there is the rate of consumption of coke per ton of iron produced, which is probably the most frequently considered, and is certainly one of the most important of the group; there is the efficiency of recovery of iron charged; and there is the efficiency of utilization of energy, both chemical and thermal, in some respects related to the former two yet in other ways independent of either. In each of these cases, the calculation can be made on the basis of the actual input of material or energy, or it may be based upon a comparison with the minimum amount of material or energy that would be required by a "perfect" furnace; that is, an imaginary ideal furnace analogous to the perfect steam engine used in thermodynamic calculations, when this furnace is operating under optimum conditions. Moreover, the furnace itself can be considered either as an apparatus for smelting iron or, taking a somewhat less common point of view, as a gas producer yielding iron and slag as by-products. Some of these efficiencies are more useful than others, yet all are instructive; for a knowledge of them not only leads to good engineering practice from the standpoint of control but also discloses limits to possible improvement in performance and indicates the lines along which improvement is most likely to be profitable. Estimates of some of these efficiencies have appeared from time to time in the literature, but many of them are open to objection because they are based on data of uncertain accuracy or because they have been calculated without due regard to the thermodynamic principles involved. Moreover, so far as the author is aware, no general survey of the blast furnace comparing its performance in all the aspects mentioned has been made.

Jan 1, 1938

By I. H. Warren, E. A. Devuyst

The selective dissolution of pyrolusite (MnO2) in presence of goethite (FeO•OH) in aqueous ammoniacal ammonium carbamate solution has been investigated: various reducing agents were studied, in particular sodium sulfite (Na2SO3,) and hydrazine hydrate (N2H4•H2O). Sodium sulfite was found to be an unsatisfactory reducing agent for both goethite and pyrolusite, for the leaching rate decreased steadily with time to an impractical level because of the limited solubility of the reactions products. Hydrazine hydrate was an effective reducing agent for pyrolusite even at low temperature, whereas goethite required much higher temperatures for any appreciable dissolution. A 1-hr leach at 35°C dissolved 90% of the pyrolusite but only 0.1% of the goethite. An activation energy of 17.0 Kcal per mole was found for the dissolution of pyrolusite with hydrazine. A reaction mechanism for the leaching of pyrolusite with hydrazine is proposed in which a reduction reaction on the surface of the mineral is the rate-determining step. The application of ammonium carbamate to the beneficiation of ilmenite is briefly described.

Jan 1, 1973

By M. Cohen, S. A. Kulin

AT a recent symposium on thermodynamics in physical metallurgy1 two opposing theories of the austenite-martensite transformation were presented. Both theories agreed that this type of reaction involves a nucleation process which requires activation and that the activated nuclei develop into the well-known martensite plates with tremendous speed. However, there were essential differences in the two points of view concerning the nature of the nucleus and the mechanism by which the nucleus propagates. According to Cohen, Machlin, and Paranjpe,' the nucleus is a strain center with sufficient elastic energy to initiate a cooperative displacement among the atoms of the parent phase when a sufficiently low temperature is reached. This displacement propagates as a wave in shear-like fashion to transform the austenite into martensite without benefit of diffusion. On the other hand, Fisher, Hollomon, and Turnbull3 regard the nucleus as a solute-poor region (in the austenite) of a size which becomes supercritical relative to coherent growth into martensite when an appropriately low temperature is reached. This growth process is taken to be an atom-by- atom transfer from the receding austenite lattice to the advancing martensite lattice through the coherent interface that exists between the two phases. The present paper is not conceded with the divergent views as to the nature of the nucleus but describes some critical experiments which differentiate between the two proposed mechanisms of propagation. Fisher' has summarized the latter issue in the following way: According to the cooperative displacement theory, the speed of formation of mar-tensite plates should not be decreased by lowering the temperature, and martensite should form with extreme rapidity at very low temperatures; whereas with the alternate growth process, the speed of the martensite transformation should be retarded at very low temperatures, decreasing to zero at the absolute zero. The atom-by-atom growth mechanism predicts a marked slowing down of the reaction rate with decreasing temperature because the rate of self-diffusion in the austenite is involved in this picture. For example, Fisher, Hollomon and Turn-bull5 estimate that the activation energy for this growth process in steel is (0.34)2(0.36)* times the activation energy for self-diffusion in y-iron. The two most recent determinations of the latter quantity are 67,900" and 74,2007 cal/mol, which may be averaged as 71,000 cal/mol. This, in turn, gives a value of 3000 cal/mol for the activation energy of the atom-by-atom process, and hence the rate of growth should vary as e 8,000/RT where R is the gas constant

Jan 1, 1951

By Samuel Shallcross

THE principal function of the Bell limestone mine, of the American Lime & Stone Co., at Bellefonte, Pa., is to supply raw material to the company's modern rotary kiln plant at Bellefonte. Because mining costs are naturally higher than many open quarries with more favorably lying strata, it cannot compete, except to a limited extent, in the markets for road material and fluxing stone. In the broad sense, mining does have an advantage over the average open quarry when the end products are designed for and controlled by process and final inspection for the exacting demands of the industrial and chemical markets. Approximately 80 per cent of the output of the Bell mine is sold in the industrial and chemical markets. And as higher standards are set each year for construction and agricultural work, the remainder of the mine output goes to these two classes. Mining produces more fines than open quarries, and these fines are difficult to market; on the other hand, owing to absence of contaminating clay and impure rock, a greater percentage of the output of a mine is marketable. Because of the great production of fines, rotary kilns for lime burning are necessary when the stone must be mined. In 1921 the American Lime & Stone Co. operated 19 quarries and 72 lime shaft kilns spread over an area of 40 miles between Bellefonte and Altoona, Pa. At that time the line-production capacity of the 72 kilns amounted to approximately 700 tons per day. After 15 years the company operates three rotary kilns and six shaft kilns, with a combined output of approximately 500 tons of lime per day, concentrated in its single Bellefonte plant (Fig. 1). Its only stone-producing plants are now the limestone mine at Bellefonte and a construction-stone open quarry at Union Furnace, near Tyrone, Pennsylvania.

Jan 1, 1936

By J. S. Bryner

INTRODUCTION IN the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light microscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silica1,2 replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/3 in. diam 200-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. DESCRIPTION OF METHOD The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper 1 X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1948

By O. N. Carlson, H. A. Wilhelm, H. E. Lunt, J. M. Dickinson

On the basis of data obtained from microscopic examination, melting observations, cooling curves, X-ray analyses, and resistance measurements, phase diagrams have been proposed for the Th-Cb and Th-Ti alloy systems. Both are simple eutectic systems and have no terminal solid solubility or intermediate phases. The eutectic between thorium and columbium occurs at a composition of about 8 wt pct Cb and a temperature of 1435°C. The Th-Ti eutectic occurs at 1190°C at the composition 12 wt pct Ti. No change was observed in the transformation temperature of thorium in either system or in the titanium transformation. RECENT study of thorium and its alloys has been promoted because of the possibility of employing this metal in nuclear reactors. Their corrosion resistant properties, nuclear characteristics, and high melting points put columbium and titanium among the many metals being employed in the study of thorium alloys. Since a knowledge of the phase relationships would be important in the application of such an alloy, investigations were undertaken to propose phase diagrams for the Th-Cb and Th-Ti systems. Experimental Procedures Thorium metal sponge was specially prepared for use in this investigation. Carbon in a quantity less than 0.04 wt pct was the principal impurity. There was also less than 0.01 pct each of iron, calcium, zinc, aluminum, and nitrogen in the thorium. Columbium, both as a powder and sheet metal, was obtained from the Fansteel Metallurgical Corp. The manufacturer's specifications indicated that the metal contains less than 1 wt pct total impurities. An analysis of the metal showed approximately 0.18 pct C in the powder and less than 0.05 pct C in the sheet. The titanium used was commercial sponge, reported to be 99.5 pct Ti. An analysis showed that this metal contained 0.2 pct Fe. Preparation of Alloys—Since the metals used in this investigation are reactive and might become contaminated on melting in a refractory crucible, the alloys were prepared by arc melting. The titanium sponge was employed in the form of small lumps while the columbium additions were made either as pressed pellets of powder or as clippings from sheet. The alloying material and the thorium sponge were melted together under argon in conventional arc melting equipment employing a tungsten electrode and a water cooled copper crucible.

Jan 1, 1957

By W. Robert Power

Dimension stone is considered by many the premium material for beauty and durability in institutional and monumental construction. Nonetheless in the United States it commands an ever decreasing share of the total market. At the beginning of the century dimension stone accounted for more than half the stone produced in the United States, but by 1974 it accounted for little more than 0.2% and the number of producing quarries and finishing plants had greatly reduced. This decrease in use is accounted for in part by competition from cheaper materials, but another factor seems to be the demand by many designers for uniformity and exact repetition of modular units in construction. Even where stone is used in large buildings modem architects want blandness of pattern and uniformity of color in the stone. Because most natural stone contains variations in color and pattern great strain is put on the quarriers to overcome this and produce a uniform product. This results in increased costs, increased waste at the quarries, and consequently increased price in the market. In spite of this, stone is still looked on as the most prestigious of building materials and its aesthetic appeal is born out by the many simulated stone patterns found in synthetic materials. End Use and Specifications The principal uses of dimension stone are in building construction and monuments. Other uses include flagging, curbing, paving, mill-stock slate, roofing slate, laboratory furniture, and refractory brick. Because many of these uses overlap, an orderly classification of dimension stone uses is most difficult. Various classifications have been used by Cumer (1960), Barton (1968), the U.S. Bureau of Mines yearbooks, and the Building Stone Institute (Anon., 1972).

Jan 1, 1975

By R. P. Abendroth

The hydrogen-water vapor ratio at which Fe-Cr alloy, chromium oxide, andiron chromite coexist in equilibrium was determined between 900" and 1200°C. A thermogravimetric method was used to determine equilibrium conditions. The results fit a straight-line relationship in the temperature region studied, and are given by Reduction experiments were also performed to confirm the results of the equilibrium investigation. ThE oxygen pressures at which Fe-Cr alloy, chromium oxide, and iron chromite coexist in equilibrium have been previously determined by Boericke and angert,' Morozov and Novokharski,' and Katsura and uan. Only one determination (at 1300°C) was made by Katsura and Muan, but it agrees with the results of orozov and Novokharski. The results of Boericke and Bangert, however, differ appreciably from the results of these investigators. Previous studies have assumed that the equilibrium metallic phase is pure iron, but Dahl and Van vlack have shown that the iron contains from about 1 wt pct Cr at 1000°C to over 2 wt pct above 1300°C. The chromium oxide also contains a small amount of iron in solid solution. In the present study, hydrogen-water vapor mixtures were equilibrated with the condensed phases, using a therrnogravimetric method to determine equilibrium conditions. The reaction can be written EXPERIMENTAL General Procedure. The starting material was a sintered pellet of Fe2O3-Cr2O3 solid solution with a hole in the center, and was placed on a fused silica hook. This assembly was raised into the preheated hot zone of the furnace in a helium atmosphere, hooked onto a fused silica hangdown suspended from one arm of an Ainsworth Model RV-AU-1 recording balance, and the starting weight determined. A flowing hydrogen-water vapor atmosphere was then exchanged for the helium by evacuation, and the sample reduced until the weight loss indicated the sample composition to be in the alloy-Cr2O3-chromite field. The tem- perature was adjusted incrementally until constant sample weight was achieved for several hours, to within 0.02 mg. A hydrogen-water vapor atmosphere of different composition was then admitted, and the same procedure carried out. At the end of a series of determinations, the sample was examined by X-ray diffraction to verify the presence of the desired phases. Microscopic examination of the silica hook showed no interaction with the sample, nor did it lose any weight. Several criteria were used to insure equilibrium besides constancy of weight. For a given hydrogen-water vapor composition, equilibrium was approached from both oxidizing and reducing sides by varying the furnace temperature slightly. The resulting slow weight loss or gain was observed for several hours. Constant weight could be re-established by returning to the original furnace temperature. The last criterion used was varying the relative amounts of the phases by further reduction or oxidation, and observing any changes in temperature required for constant weight for a given hydrogen-water vapor atmosphere. None were observed. This procedure was essentially the same as approaching the equilibrium from oxidizing and reducing sides, but larger weight excursions were carried out. Sample Preparation. Reagent-grade Fe2O3 and Cr83 powders were mixed in the desired proportions and heated in air at 1250°C for 2 hr. The mixture was re-ground and heated in air overnight at 1250°C. X-ray diffraction showed complete solid-solution formation as a result of this procedure. The solid solution was then pressed into l/2-in.-diam pellets using Carbowax 4000 as a binder. The hole was drilled in the center, and the pellets were sintered 24 hr at 1250°C in air on a bed of Fe2O3-Cr2O3 of the same composition, contained in an alundum boat. After cooling, the pellet surfaces were abraded with 310 paper to remove any surface compositional differences, such as loss of Cr2O3. Chemical analysis of the sintered pellets was 67.16 wt pct CrP3 and 33.02 wt pct Fe203. Atmosphere Generation and Control. The hydrogen-water vapor atmospheres were generated by passing Matheson ultrahigh-purity hydrogen, with no further purification, through two water bubblers contained in a constant-temperature water bath. Since the water-vapor dew points required in this study were below room temperature, the bath was insulated, and was cooled by thermoelectric-immersion devices. The bath temperature was controlled to 0.0l0C. Since rather high flow rates of about 900 ml per min were used through the furnace tube, an independent check of the dew point was made to insure saturation of the hydrogen by the water vapor. Although the dew point could only be determined to within 1/2"C, the determined dew points agreed with the water-bath temper-

Jan 1, 1967

By Edgar Shepard

THE interest of the Federal Government in improvement of water-ways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duty of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investi-gations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as "308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects.

Jan 1, 1940

By N. G. W. Cook

When an excavation is made underground the original rock stresses are removed from the surfaces of the excavation. These surfaces converge to partially close the excavation and the superincumbent rock mass moves down towards the excavation. If the convergence of the surfaces of the excavation were controlled, energy generated by their motion against the controlling forces could be extracted. Since the total forces in the rock mass are not significantly affected by the excavation, stress concentrations arise around the excavation, which compensate exactly for those stresses no longer transmitted through the excavation. These phenomena give rise to two general principles which provide the basis for analyzing the effects of making any underground excavation. The first of these is that the total force resulting from the stresses across any plane in the rock, including any plane through the excavation, must be the same before and after the excavation is made. The second of these is that energy must necessarily be released as a result of making an underground excavation. It is instructive to consider the implications of these two principles for two extreme cases of material behavior between which the actual behavior of rock must lie, namely, the behavior of a fluid and the behavior of an elastic solid. For the purpose of analysis in this paper, an underground excavation is defined as an excavation in which the smaller horizontal dimension of any open void at a particular horizon is less than the depth of that horizon below surface. In the case of a fluid, any unsupported excavation would fill immediately, as a fluid cannot sustain shear stresses. For the same reason, stress concentrations could not arise and the forces across any plane would necessarily be the same before and after excavation. If the filling of the excavation were controlled by forces applied to the surfaces of the excavation, an amount of energy equal to the product of the fluid pressure

Jan 1, 1967

By P. D. Merica

The remarkable phenomena exhibited by the aluminum alloy known as duralumin were discovered during the years 1903-1911 by A. Wilm1,2 and have been described by him and by others. 3 4 5 6 The unusual feature of this alloy is the fact, as was shown by Wilm, that it can be hardened quite appreciably by quenching from temperatures below its melting point followed by aging at ordinary temperatures, which consists merely f allowing the material to stand at these temperatures. The hardness is not produced by the quenching alone but increases during the period of aging, which may be from one to three days. Cohn3, 5 gives data showing the increase of hardness of duralumin during aging, after quenching in water from about 450° C. Upon annealing, the alloy so hardened by aging is softened exactly as is hardened steel. The composition of this alloy usually varies within the following limits: Copper, 3 to 4.5 per cent.; magnesium, 0.4 to 1.0 per cent.; manganese, 0 to 0.7 per cent.; aluminum, balance; iron (as impurities), 0.4 to 1 per cent.; silicon, 0.3 to 0.6 per cent. Its density is about 2.85. It is used only in the forged or rolled condition. This alloy has been produced for some years commercially and is in demand for the fabrication of parts for which both lightness and strength are required, such as for aircraft. Its tensile strength will average 50,000 to 60,000 lb. per. sq. in. (3515 to 4218, kg. per sq. cm.) after appropriate heat treatment, such as that described by Wilm.

Jan 6, 1919