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By E. Posnjak

IT is rather the general belief that acidified solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no. oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by, passing air for 3 hr. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will be proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2. His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 1, 1927

By F. J. Williams

BARITE, naturally occurring barium sulphate, is the chief barium mineral that is produced commercially. Barite is also called "barytes," "heavy spar," sometimes "baryta" and, locally in Missouri, "tiff." Pure barite is white, opaque to transparent. It crystallizes in the orthorhombic system, frequently with twinning. Impurities cause a wide variation in color, commonly buff, gray and white with irregular reddish iron stains. Less frequently found are shades of yellow, green, blue, brown, and black. The rock is brittle and breaks with an uneven fracture, although specimens from some of the residual deposits, particularly in Missouri, appear to have a cleavage due to the separation of the different layers of deposition. The hardness varies from 2.5 to 3.5 on Mohs' scale and different localities are said to produce either "hard" or "soft" barite. This generally refers to the ease of grinding of the product. The specific gravity of pure barite is 4.5 and this will vary downward, depending on the impurities present. The mineral has a white streak and a pearly to vitreous or sometimes stony luster. Pure barite contains 65.7 pct BaO and 34.3 pct SO3. Witherite, native barium carbonate, is not mined in the United States at the present time although a number of occurrences have been reported. A small quantity of witherite has been removed from a mine at El Portal, California, but the area high in witherite was small and soon depleted. The bulk of the deposit is predominantly barite. Great Britain is the world source of witherite and small quantities are imported into the United States. DISTRIBUTION OF DEPOSITS Occurrence of barite is widespread; it has been reported on all the continents and in all the major countries of the world. Deposits vary from those containing millions of tons down to scattered rock fragments

Jan 1, 1949

By James Norman, E. W. Gieseke

Spodumene is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content, it might be a desirable constituent of glass batches. The use of spodumene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components. The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manganese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li²O on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston,S the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3The methods described in the second publication3 did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted. Study of Method of Flotation Separation Most of the work on concentration of spodumene was done with rock from near King's Mountain, North Carolina. Rock from two

Jan 1, 1942

By James Norman, E. W. Gieseke

Spodumene is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content, it might be a desirable constituent of glass batches. The use of spodumene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components. The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manganese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li²O on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston,S the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3The methods described in the second publication3 did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted. Study of Method of Flotation Separation Most of the work on concentration of spodumene was done with rock from near King's Mountain, North Carolina. Rock from two

Jan 1, 1942

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.' sturkey,' however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.' The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,' but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

By E. Posnjak

IT is rather the general belief that acidified, solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as. cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by passing air for 3 hr.. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will bee proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2 His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 12, 1926

By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-' the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:' and, if some simplifying assumptions about particle shape are allowed, the total number of particles.'2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.' Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By Richard W. Lodge

Ix the crucible-method of assaying ores for silver a certain amount of litharge is essential to supply sufficient lead to collect the precious metals. The object of this paper is to point out that the use of a .large excess of litharge in the assay of some ores will give results for silver that are uneven as well as low. So far as I know, however, an excess of litharge does not affect the results obtained in the crucible-assay of ores for gold. The main reasons for using, in the crucible-assay, much more litharge than is required to give the necessary lead button are : 1, its action as a flux; 2, its action as a desulphurizer; and 3, its action as an oxidizer, especially on metals like copper and nickel, whereby they are forced into the slag as oxides and thus prevented from passing into the lead button. Hence, by the use of much litharge in the crucible-assay more-ore can often be taken than in the scorification-process, and a lead button obtained which can possibly be cupelled at once or after a single scorification. The method is specially advantageous with an ore carrying much copper or similar impurity and poor in silver, when the assayer does not wish to resort to a wet-analysis for the determination of the silver. It is well known that some ores give better results when assayed by the scorification-method, while others give better results by the crucible-method. For several years I have noticed that, when much litharge was used with certain sulphide and arsenical ores, the results were considerably lower than when the scorification-method was used. This fact was more forcibly brought out in connection with certain work carried on this year by Messrs. H. A. Frame and

Sep 1, 1907

By Edmond S. Miksch

The morphology and growth rate of ice grown in supercooled water are markedly affected by convection of the water. A dendritic ice sheet with water flowing past the dendrite tip exhibits deflection of the dendrite spine toward the upstream direction, accelerated growth of secondary spines on the upstream side, and suppression 01" secondaries on the downstream side. Flow causes a thin disk to become corrugated, the corrugations being parallel to the flow. Flow causes an increase in the growth rate of the ice. IF a small seed of ice is placed in slightly supercooled water, it grows initially as a disk with the axis of the disk parallel to the c axis of the ice crystal.' It appears that growth in the c direction is inhibited, while growth occurs with equal facility in all directions in the basal plane. It appears that growth rate as a function of interface temperature is very nearly equal for all directions similarly oriented relative to the c axis. Subsequent to the discoid growth, branching occurs and dendrites develop. The primary dendrite spines grow parallel to the six equivalent a axes of the crystal. Secondary, and in some cases, tertiary spines also grow in these directions. The highly anisotropic: dendritic growth indicates that there must be some finite difference of growth rate for different directions in the basal plane. These differences must be quite small, however, since if they were large, the discoid mode would not occur. Hence, it was expected that the dendrite growth direction could be deflected from the crystallographic direction by perturbation of the thermal field at the dendrite tip. Experiments were done in which perturbation of the thermal field was accomplished by causing the supercooled water to flow past the dendrite tip. The flow direction was perpendicular to the c axis of the crystal, and was perpendicular to the primary spine of the unperturbed crystal. Supercooled water was supplied by a 15 cm cubical copper box, which was refrigerated and insulated so it could cool water to temperatures down to —2oC, and maintain the temperature constant to O.l°C for the duration of a run. A lucite channel of rectangular cross-section, 12 by 24 mm, was mounted horizontally in the box, with one end open so water could flow into it, and the other end leading out through the wall of the box to a length of tubing leading: to an orifice plate 123 cm below. cnunMn s MIKSCH, MemberAiMe, formerly Research Associate, Research Associate, Fig. l(b)—Vertical section of apparatus A horizontal cross-section is shown in Fig. l(a), and a vertical section is shown in Fig. l(b). Means for observing the ice are shown in Fig. l(a). Collimated light passes through the ice sheet and forms an image on the ground glass screen. A lucite box containing dry air was employed to prevent condensation. Ice of the desired orientation was provided by the seed holder shown in Fig. l(b). This device was made of lucite, and had a reservoir in which ice could be frozen by placing it in a freezer. This reservoir com-unicated with the outside only through a narrow gap between two sheets of lucite. The seed holder (after ice had been washed off its exterior) was immersed in the tank of supercooled water, the narrow gap terminating in a slot in the top of the flow channel. Ice growing through a thin water layer in the gap between the two sheets of lucite was oriented so its c axis was perpendicular to the sheets. This orientation is an application of a growth phenomenon2 which causes ice growing along a smooth solid surface in supercooled water to orient itself so its c axis is normal to the surface. After the ice grew into the channel, further orientation was necessary, since the direction of the a axis

Jan 1, 1970

By Leroy Gardner

EVERY reader of this paper is well aware of the fact that the prolonged inhalation of large amounts of free silica dust results in fibrosis of the lungs, and that other inorganic dusts, except those of asbestos and the mineral poisons, are thought to be relatively harmless. But probably few have had opportunity to visualize the effects of silica, asbestos and other minerals upon living tissues. The ideal demonstration would be based upon sections of lungs from human beings that had inhaled com-parable concentrations of different dusts for a unit period of time. Such material is generally difficult to obtain and in some instances is of ques-tionable value because the subject has been exposed to more than one kind of dust. A demonstration could be prepared from the lungs of animals. However, so many months or even years are required to com-plete the exposure to each kind of dust that enough material has not been accumulated. For a general survey of the action of different types of dust, I am therefore compelled to use the tissues of animals that have been injected with suspensions of dust particles. The injection method offers certain advantages. The quantity, the particle size and the state of dispersion can be controlled with sufficient accuracy so that the tissue responses to different minerals can be accu-rately compared. The method insures contact between the tissues and the mineral particles; protective mechanisms, which may prevent the inhalation of certain types of foreign body, never come into play. If the pathway of injection be one that minimizes nonspecific injury, the tissue responses may simulate those produced by inhalation but they develop somewhat more rapidly. It should always be remembered that injection methods merely demonstrate the capacity of various kinds of minerals to provoke reaction in the tissues; whether the same substances are inhaled from atmospheric suspension and accumulate in the lungs in dangerous quantities can be demonstrated only by inhalation.

Jan 1, 1938

By Norman D. Fitz Gerald

THE growth of domestic requirements for motor fuel has been phe-nomenal, rising year after year in a fashion almost unique among com-modities, resisting depressions and forging rapidly ahead in times of prosperity. Consumption advanced from 226 millions of barrels in 1925 to 522 millions of barrels in 1938; or 130 per cent. The economic influ-ences generating and sustaining this demand are of vital concern to the petroleum industry. The general factors affecting utilization of motor fuel are well known but it is the purpose of this paper to employ the recently developed technique of economic dynamics to describe them mathematically. Such problems in economic analysis are complicated by the freedom of all the variables to fluctuate, their mutual interdependence, changing incidence upon one another, and the nonquantitative character of some of them. Economic quantities and relationships, unlike those of the physical world, are continuously changing and this dynamic characteristic is both a distinguishing and confusing feature in economic research. The com-plexities of the problems require application of the analytical devices of mathematical statistics to uncover the probable relationships between factors. The procedure employed is to formulate a logical relationship linking the dependent to the independent variables, and then simul-taneously, rather than sequentially, determine their separate effects by multiple correlation. This transformation of common knowledge to quantitative terms makes it possible to measure the probable effects of changing conditions upon requirements, assisting in the sound interpreta-tion of economic policies. The utility of the results of such dynamic analysis is in sharp contrast to the sterility of the trends and other simple empiricisms of descriptive statistics. It is not intended in this study to throw light on the reasons why any motor fuel at all is consumed; but to discover relationships explaining why more was consumed at one time than at another. Specifically the prob-lem is confined to the measurement of the influences of statistically

Jan 1, 1940

By A.E. Martin, Gerhard Derge

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

Jan 1, 1943

By A. E. Martin, Gerhard Derge

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

Jan 1, 1943

By A. E. Martin, Gerhard Derge

IF the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of diffusion, and electrical conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented as Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags of the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. REVIEW of LITERATURE In 1906 Aiken1 obtained a patent for a continuous process of producing iron electrolytically by passing a direct current through a bath of FeO-SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

AN intermetallic compound, Ni3A1, has an ordered fcc structure of type Ll2, and shows peculiar dependence of the yield stress upon temperature; i.e., the yield stress increases by a factor of six upon raising the temperature from 77" to 900K1, 2 This compound is technologically important, since many nickel-base superalloys owe their high-temperature strength to the peculiar yield stress behavior of Ni3Al. The only study of the elastic behavior of this compound was made by Davies and Stoloff,1 who determined Young's modulus of poly crystalline Ni3A1 between 300" and 730°K. The determination of single-crystal elastic constants of Ni3A1 is therefore of interest in connection with dislocation dynamics and is reported in this paper. A single-crystal specimen, 1 by 1 by 3 cm, was cut from an ingot generously supplied by Dr. B. H. Kear of Pratt & Whitney Aircraft. Following initial machining with a Servomet and a surface grinder, the specimen was etched and annealed at 1100°C for 5 hr in vacuum followed by furnace cooling. Two parallel faces were oriented normal to within ±l deg of a [I101 crystallographic axis by the back-reflection Laue technique. The parallel faces were hand-lapped, etched, and polished by the usual metallographic procedures. Final thickness along the [I101 axis was (0.9325 * 0.0005) cm. Chemical analysis gave an average composition of 87.35 pct Ni. Total impurity content is esimated to be no more than 0.1 pct. The elastic constants were calculated from measurements of ultrasonic waves which were propagated along the [110] axis. A longitudinal wave and two shear waves whose displacements are aligned along the [ 110], [li~], and [001] directions, respectively, are necessary in order to completely specify the three elastic constants. Two 3/6-in. quartz transducers were bonded to the parallel faces of the sample with ~ac-seal.3 Although this bond was sensitive to thermal shock, it performed satisfactorily over the entire temperature range for both longitudinal and shear wave propagation. A frequency of 5 mHz was employed in the method of Williams and Lamb4 in order to measure the absolute value of the ultrasonic velocity. The pulse-overlap technique of Mcskimin5 was also used at this frequency in order to determine the shift in the ultrasonic velocity

Jan 1, 1970

By Robert L. Akre

When Marco Polo visited China in the 13th century, no one knew what black powder was except the Chinese; they knew enough to make dazzling fireworks with it. But the realization that black powder could also do useful work came much later and, like all important discoveries, it altered the course of history. It was in the 14th century that black powder was first used to break rock in a very crude way; there were no drills and the powder was simply poured into cracks and exploded by setting it afire. Because its energy value was pretty low, the need for something more powerful was felt when the industrial revolution began. In the 1850s, miners began experimenting with liquid nitroglycerine on a limited scale. This was a very sensitive and dangerous explosive. Fortunately in the 1860s, Alfred Nobel succeeded in stabilizing nitroglycerine by absorbing it in kieselguhr-and a new product, dynamite, was born. With it, miners were able to unleash the great energy of nitroglycerine for blasting purposes. But dynamite was still a very sensitive explosive. In subsequent years, other explosives of various strengths and characteristics were developed, such as blasting gelatin, gelatin dynamite, ammonia dynamites, (all containing some nitroglycerine or nitrostarch), and liquid oxygen explosives. These products and their variations supplied the blasting trade for many years. A grained ammonium nitrate product containing some carbonaceous material entered the market in the 1930s. This explosive had below-zero sensitivity-meaning: a No. 6 blasting cap imbedded in it would not detonate it. A more sensitive initiator, called a primer, was needed to detonate this mixture. From Rags to Primacord to Solid-State The first initiator for an explosive charge was probably a rag slowly burning its way to the charge; this method was quite unreliable. Then came the burning fuse, which was an improvement. Next was the nonelectric blasting cap initiated by a fuse. With these initiators, a miner needed quick reflexes and good legs; upon lighting the fuse, he had to run immediately for cover. Development of the electric blasting cap that allowed for accurate timing eliminated this hazard; the electric cap, however, introduced other safety problems because of its susceptibility to extraneous electricity, e.g., ground currents, lightning, and static electricity. These caps also became available in millisecond delays. Development in the mid-1930s of Primacord, a detonating fuse insensitive to electrical currents or impact, further reduced blasting hazards, and is generally acknowledged as the safest known means of initiation. Eventually, Primacord millisecond connectors also became available for delay patterns in blasting. In the mid-1960s, the Primadet delay was introduced; it is a practical nonelectric detonator system that offers the precise timing of electric blasting caps-and is immune to the hazards or effects of extraneous electricity. Recently, Research Energy of Ohio, Inc. introduced a new type of solid-state blasting machine that combines a sequential timer and delay caps. It enables the efficient breakage of rock with a minimum amount of shock, ground vibration, and noise. Improvements in Blast-Hole Drilling World War II created an enormous demand for coal and other minerals in the U.S. and elsewhere. Great efforts and large amounts of capital were spent to find new mineral deposits and develop better mining methods. But while mechanization in mining proceeded at a rapid pace particularly in open-cut work, there was a definite lag in developing new or improved machines for drilling blast holes. The industry continued to depend largely on horizontal, churn, and pneumatic drills. No better machine was available for large scale production. The need for improvement in this phase of mining became more acute in the post-war years. Despite efforts toward further mechanization, mining costs rose rapidly because of mounting inflation and increasingly high wages. In most operations, drilling and blasting the overburden became the principal item of cost. Therefore, whatever size holes were being drilled, the holes had to be spaced so that any foot of the bore hole could be loaded with the maximum load required for the number of cubic yards of material that each foot of the hole was carrying. With the smaller holes that were being drilled, the proportion of drilling cost to the total drilling and shooting cost was much higher than it would have been with larger holes (because of the closer spacing required by smal-

Jan 1, 1977

By R. A. Pasternak, B. Evans

In an ultrahigh-vacuum study of the sorption of nitrogen by niobium* resistivity data for this metal have been obtained as function of temperature and of low nitrogen concentrations. The ultrahigh-vacuum system in which base pressures of about 5 x l0-10

Jan 1, 1965

R. B. BRINSMADE, Ixmiquilpan, Hgo, Mexico* (written discussion). As the discussion of Mr. Graton's paper by Messrs. Norris, Patterson, and Crane has been from the standpoint of the mineral land-value owners, a few remarks in the interest of the "under dog"-the average taxpayer and citizen-may prove timely. In my discussion of Doctor Raymond's Paper1 and of the papers of Messrs. Gibson2 and Godson, 3 have endeavored to demonstrate, from both political economy and history, that our existing system of unrestricted private ownership of land is incompatible with equality of economic opportunity and, therefore, subversive of our democratic political institutions. In Mr. Graton's paper, the same land problem is important, though camouflaged by the failure of the Federal income tax laws to distinguish between land and capital, in the requirements for valuation, or between earned and unearned incomes in the levying of taxes. I disagree with Mr. Graton's statement, on p. 2967, as follows: The immense majority of mining ventures are failures. A multitude of disappointments is relieved by occasional success. Were it not for the chance of great rewards, all the vitally necessary but mainly unremunerative work of exploration would not be undertaken. In contrast with nearly all other fields of endeavor, it is altogether unlikely that, on the whole, the gains in the successful mining ventures suffice to offset the losses in the unsuccessful.

Jan 3, 1920

I HIT the ceiling when I opened my November MINING ENGINEERING and after waiting a week to cool off I' still find it necessary to express my resentment of the gross libel embodied in the editorial introduction to Norman Stines' legitimate criticism of my paper on "Russia's Mineral Potential" (p. 949). The underlying thesis of my article, and a point that I tried to make even more clearly in my oral presentation at the St. Louis meeting last February, is that we should not over estimate the present and near-future mineral production of the USSR. The words that I resent in your boxed introduction are: "Opinions range from those presented by Paul Tyler ... to those of Norman C. Stines . . ." This is not merely an understatement that can be defended by admitting that the range goes much farther to the left, beyond me. It represents the appraisal that 90 pct of your members will carry away, namely that I am not only an incompetent observer-which may be true-but always that my bias is to applaud the efficiency of the beasts in the Kremlin-which is not true. Notwithstanding my efforts to clarify the record I now find myself branded as being at the opposite pole from 'Mr. Stines among the red-eyed worshipers of Communism or at least among the timid souls that shake in their boots in the belief that the Soviet system has created an invincible as well as an evil menace to the decent peoples of the world. My ideas are somewhere in the middle ground between Mr. Stines' complaisance or contempt and the exaggerated fears of several other observers whose views have received wide acceptance. PAUL M. TYLER MINERAL TECHNOLOGIST & ECONOMIST 5005 EDGEMOOR LANE, BETHESDA, MD. The introductory paragraph to Mr. Stines' criticism of Mr. Tyler's article (Russia's Mineral Potential, June issue MINING ENGINEERING, page 494) is erroneous as pointed out in author Tyler's letter above. In his article he objectively presented an estimate of the mineral position of the Soviet based on the statistics available to him which sources are credited in the first paragraph of his article. We happen to know that, Mr. Tyler was reluctant to prepare the article for the Mineral Economics Division sessions at the 1951 Annual Meeting and did so only because of his loyalty to AIME. It was thought that this article would be a basis for discussion of this important subject at the Annual Meeting. We apologize to Mr. Tyler for any embarrassment our introduction, may have caused him. Editor

Jan 1, 1952

By Jacob T. Wainwright

This stove has been designed to meet the requirements of a fur nave that must be operated with either a reducing or a neutral flame ; and more particularly to make feasible the operating of re duction-furnaces with the cheaper grades of gas-fuel, which has heretofore been impracticable. In general, cheap gas-fuels result from incomplete combustion, and, being suited for further combustion, answer very well for heat ing purposes; and high temperatures may be attained with them, when they are used in conjunction with regenerative stoves. But, in operating a reduction-furnace, a high temperature is not the only requirement. It is also necessary that the fuel shall not be cansumed beyond a certain degree, in order to insure a re ducing flame for the reduction-process ; consequently, it becomes necessary to dispense with combustion as much as possible previous to the use of the fuel-gases in the reduction-furnace. Moreover, these gases must be preheated to a high degree, in order that a sufficient temperature may be maintained in the furnace; and, since this preheating cannot be accomplished by a previous, partial combustion of the gases themselves, it follows that the stoves for pre heating these gases should be heated to as high degree as it is pos sible to attain with an inferior fuel. This result can best be accom plished by complete combustion of the heating gases, and is further facilitated by preheating all of the air and gas used for this com plete combustion. It is more particularly desirable to preheat the air, since the combustible gases used may generally be obtained directly from the furnace, or gas-producer. The reducing gases, escaping from a gas-fuel reduction-furnace, are capable of considerable further dilution with air to secure com plete combustion, and consequently may be utilized for heating the stove to a high temperature, provided the air be sufficiently preheated.

Jan 1, 1889