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By J. E. Johnson

It is the purpose of the present paper, while not excluding chemical considerations, to deal more extensively with some of the physical and mechanical aspects of the blast-furnace process, and to point out its dependence, in these respects, on well-known laws. The quantity and cost of ore and flux required to make a ton of iron being determined by circumstances over which the furnace-man, under given conditions as to quality and quantity of product, has commonly little control, the principal item of cost, apart from the saving of labor, which he can aspire to reduce, is that of fuel. To determine the limits of possibility in this direction is clearly the first step in a practical inquiry; and this step is represented herewith in Fig. 1, a diagram showing the total useful effect obtained from a pound of fuel under various conditions, and thus permitting direct comparison, under any given conditions, between actual results and the maximum possible results. The following statements will explain the basis upon which this diagram has been constructed. One pound of fuel, containing 90 per cent. of fixed carbon (which represents average conditions), is taken as the unit. The degree of oxidation of the carbon is measured by the ratio of the two oxides of carbon contained in the top-gases. It is necessary to remember that a considerable quantity of carbon is brought in as carbon dioxide by the flux, and to take account of it and of its condition. It is here considered that the carbon dioxide liberated by the limestone does not affect the analysis of the top-gases, and that the ratio of CO to CO2 will remain unchanged by the addition of limestone; enough CO, being reduced by the solution

Jan 1, 1906

By A. N. Winchell

In connection with law suits between mining companies at Bingham, Utah, a few years ago, the writer made petrographic studies of more than 1400 rock and mineral samples in thin sections, and also careful studies of their field relations. In petrographic studies, even when an area is studied intensively, attention is commonly centered very largely on the unusual features of special interest, so that the relative abundance of rock types (or minerals or textures) can only be determined by a study of map areas outlined largely by field methods, and cannot be based directly on microscopic work. It is very uncommon, and usually impossible, to take samples at regular short intervals along and across formations. It is precisely because such methods were used at Ringham that the work presents a rare opportunity for determining, on a microscopic basis, the relative abundance of rock types and the continuity of gradations between rock types. At the same time, a study was made of the alteration of sediments under the influence of igneous intrusions, with results that are believed to be of interest and importance. • Sandstone-limestone Gradation The sedimentary rocks of the Bingham district are chiefly sandstones, with some beds of limestone, all now lying with their strike nearly east and their dip nearly north at an angle of about 30°, near the surface. The limestone beds are remarkably irregular in thickness in some places, but usually change very slowly in composition along the strike. However, the most interesting results are obtained from a study of a section across the beds at right angles to the strike. In some places, such sections show the usual alternation of pure sandstone with nearly pure limestone, in the simple manner assumed in most geological discussions.

Jan 1, 1924

By J. L. Dumanoir, Maurice Martin

The induction-electrical log is a combination of a SP curve, a short normal curve, and an induction log; all three logs being recorded simultaneously in a single run. The spacing of the short normal is 16 in. The induction log is designated as 5FF40, which means that the sonde involves five coils and a focusing system, and that the distance between the main coils is 40 in. Examples of induction-electrical logs are shown in Figs. 13 and 15. The right-hand track contains the induction conductivity curve. The scale of this curve is linear with the units of conductivity, i.e., mhos/m or millimhos/m (mmhos/m), increasing from right to left. The same curve can be read in the reverse direction as a resistivity log, with a hyperbolic scale. In the middle track, the solid curve represents the short normal. (An amplified short normal is also shown in Fig. 15). The dotted curve is the resistivity curve of the induction log, i.e., the reciprocal of the conductivity curve, recorded with the same linear scale as the short normal. The SP is in the left-hand track. In this combination, the SP curve and the 16-in. normal are the essential correlation curves, as in the conventional electrical log. The induction log provides a more accurate and detailed record of formation boundaries than the conventional log, especially in hard rock territories. Furthermore, the induction-electrical log makes possible the determination of fluid content, particularly in thin beds—at least qualitatively and very often quantitatively. In such thin beds, because of the adverse effect of the adjacent formations, the responses of the conventional devices are generally doubtful and/or incom-plete. Another advantage of the new combination is that the induction log is little affected by the presence of thin hard streaks interbedded within the permeable sections, whereas such occurrences are the cause of serious distortions of the long normal and lateral curves. The evaluation of saturation from any resistivity log implies the knowledge of the true resistivity R, of the bed and of the resistivity R.. of the flushed zone, or at least of the ratio Rxo/Rc. With the induction-electrical log run in fresh mud, the 16-in. nor-mal has a smaller radius of investigation than the induction log, so that the former reads closer to R.. and the latter closer to Rt. Thus, it has been observed that the ratio of the 16-in. normal to the induction log readings can be used as a basis for the interpretation in terms of saturation, with the help of appropriate charts. The purpose of the present paper is essentially to explain this procedure and to provide the corresponding charts. On the other hand, when a formation is deeply invaded, the response of any log (in particular the induction log) depends upon the radial distribution of formation resistivities behind the wall of the hole, which itself is a function of the arrangement of the fluids saturating the formation pore spaces. This paper, accordingly, will begin with a schematic description of the distribution of fluids and resistivities in the invaded zone. Next, some essential characteristics of the induction log will be reviewed. Finally, the determination of the interpretation charts and their application will be explained. The discussion will be confined to the case of fresh muds, i.e., muds whose resistivity is at least five times as great as that of the formation waters. With the present equipment the induction log is not well adapted for logging in salty mud. The Laterolog and guard electrode log are at their best under conditions of low resistivity mud. Accordingly, when these tools were introduced a few years ago, the use of salty mud was recommended. Now, with the introduction of induction logging, spe-

Jan 1, 1958

By Nicholas J. Grant, Noboru Komatsu

Electron-micrographic studies and hardness tests were made of an internally oxidized dispersion-strengthened Cu-12 vol pct SiO2 alloy follozuing longtime annealing at elevated temperatures. The rate of coarsening of SiO2 particles and the relationship between hardness and interpavticle spacing were Dispersion -strengthened alloys exhibit a remarkable stability of structure and properties at elevated temperatures compared with conventional alloys; nevertheless, when they are exposed to high measured. The rate of coarsening of SiO2 particles is controlled by the decomposition of SiO, rather than by the diffusion rates of silicon or oxygen through the copper matrix. The mechanism of coarsening was also studied by using a diffusion-couple technique. temperatures, weakening takes place as a result of coarsening of the dispersed phase. The theoretical treatment of the coarsening of dispersed phases has been treated by Greenwood,1 wagner,, and others3 by considering the interfacial energy of dispersions and the diffusion of solute atoms. Recently, experimental work on the coarsening of relatively insoluble, finely dispersed cobalt particles in copper was reported by Livingston,4 and on aluminum oxide in nickel by Dromsky, Lenel, and Ansell;5 according to these investigations, the rate

Jan 1, 1964

By L. A. Mekler

THE recirculating furnace is primarily a heating apparatus of the convection type in which the heat-absorbing surfaces are heated by a mixture of fresh products of combustion and a portion of the combustion gases that have already given off a part of their heat in their previous passage over the heat-absorbing surfaces. In its basic conception, the recirculating furnace can be considered as a closed thermal system in which the heat-absorbing surfaces are .constantly swept by a fixed quantity of products of combustion at a given initial temperature with the gases being constantly returned to the furnace and reheated before they again enter the heating zone. Gases equal in amount to that produced by the fuel burned to reheat the circulating gases are constantly ejected from the system to the stack. The recirculating furnace is the most suitable apparatus for heating by convection where low furnace temperatures must be maintained and where only a small portion of the available heat is taken out of the gases, particularly where the maximum allowable furnace temperature is low and where the final temperature of the gases is only a few hundred degrees below their initial temperature. In such cases, recirculation not only provides a method of reducing the rather high combustion temperatures of the fuel when burned without a large amount of excess air, but, by returning to the furnace the heat content of the gases at their final temperature, recovers a large portion of heat that otherwise would have been lost through the stack.

Jan 1, 1928

By T. B. Counselman

An iron blast furnace of 1000 tons daily capacity will produce a 100,000 cu. ft. per minute of blast-furnace gas. This contains a 25 per cent of carbon monoxide, and has a B.t.u. value of about 95. gas is used primarily for heating the stoves of the blast furnace, secondarily, under boilers, for steam production. Occasionally it is used in gas engines. The raw gas coming out of the furnace carries about 10 grains of dust per cubic foot of gas, under best operating conditions. With furnace "rolling" or slipping, this quantity may temporarily be gre increased. This dust would, of course, deposit on the checkers o: stoves, or plug the burners under the boilers; therefore the gas : be cleaned. Flow Sheet The first step in the cleaning operation, as shown by the flow s Fig. 1, is a dry dust catcher, of which there are several forms, partially cleaned gas next goes to a primary wet washer, where v sprays knock down most of the solid particles. If further cleani desired, the gas may then go to electrical precipitation. Again, the removed is collected in water. Dry dust catchers reduce the dust col from 10 grains to between 4 and 6 grains per cubic foot, and rec roughly half of the total flue dust in the gas. The wet washers rea most of the remaining dust, reducing the dust content to about 1/4 per cubic foot. Electrical precipitators, if used, further reduce the content to about 0.01 grain per cubic foot of gas. The flow sheet s the dust content of the gas at various steps in the treatment and als content of solids in the water. It should be noted that some plant less water on the primary wet washer than indicated, and that ofte solids content of the scrubber water will be 300 grains per gallon, or much higher. Reasons for Recovering Flue Dust.—There are two main incentive recovering flue dust from the scrubber water: (1) the value of the (2) stream or lake pollution, where such a reason applies.

Jan 1, 1937

By B. A. Cheadle, K. P. Steward

Axial tensile, ring tensile, closed end burst, and free end burst tests were done at room tempe.vature and 300°C on three batches of Zircaloy-2 sheathing zuith different textures. Knoop hardness tests were also done on all batches. The mechanical properties of the tubes were largely dependent on the percentages of cold work, but were also markedly affected by the textures, particularly with respect to deformation behavio'r. The deformation behavior observed confirmed Picklesimer's predictions, zuhereas Knoop hardness results could be correlated with texture and yield strength anisotropy after the ,method of Wheeler and Ireland. From the mechanical properties, and from efjectiue strain values deterrlzined at the fractures using a photoqid technique, it zuas concluded that tubing witlz a single preferred orientation of radial basal poles best combines strength and ductility for any given deqee of cold work. THE mechanical properties required in collapsible Zircaloy-2 fuel sheathing for water-cooled power reactors are strength to resist wrinkling deformation by coolant pressure and ductility to accommodate a small amount of deformation in service without rupturing. Zircaloy-2 tubing during fabrication develops pre- ferred orientations of the a Zr grains due to aniso-tropic deformation behavior, and these textures markedly affect mechanical properties. Picklesimer' had predicted the deformation behavior of tubes with various textures, but the texture required to provide the optimum strength and ductility for a given degree of cold work has not been reported. To investigate this problem, tests at three transverse to axial stress ratios were done at room temperature and 300°C on three batches of Zircaloy-2 tubing covering a wide range of textures and percentages of residual cold work. Knoop hardness values were also measured to correlate with preferred orientation and yield strength anisotropy after the method of Wheeler and relland.' 1) MATERIAL For this investigation, three batches of tube-reduced tubing were chosen from the Zircaloy-2 sheathing produced for the Douglas Point Reactor. Individual tubes were 191/2 in. long, 0.600 in. OD, and 0.0165 in. nominal wall thickness. The identities of the batches, together with their textures, are shown in Table I. The tubes had the normal Zircaloy-2 composition3 of 1.5 wt pct Sn, 0.3 wt pct Fe, Ni, Cr combined with the following oxygen concentrations: Batch VII 1140 to 1390 ppm 0 Batch VIII 1400 to 1750 ppm 0 Batch IX 880 to 1320 ppm 0

Jan 1, 1968

By L. O. Brockway, W. C. Bigelow, J. A. Amy

Specimens of Inconel-X alloy solution-treated at 2050°F and aged for periods of 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F have been examined by electron microscopy and by electron and X-ray diffraction. Four minor phases were identified: titanium nitride, niobium nitride, an M23C6 complex carbide, and the intermetallic ? phase. The two nitrides were found in all of the aged specimens and in the solution-treated alloy, the y' phase formed at all aging temperatures, while the M23C6 carbide formed only on aging at 1200° and 1400°F. Variations in the hardness, rupture strength, creep strength, and yield strength of the alloy have been shown to be related to variation in the size and distribution of the particles of the y' phase within the matrix grains of the alloy, with maximum values of these properties occurring when there is a maximum amount of the phase present and a fine state of dispersion of the particles prevails. THE nickel-chromium alloys containing titanium and aluminum are widely used in applications requiring high strength at elevated temperatures. Studies on relatively simple ternary and quaternary alloys'-4 have indicated that the favorable high-temperature properties of these alloys are related to the precipitation of an intermetallic ?'-phase having a structure based On that of the Ni3A1 phase of the nickel-aluminum system. The present investigation was undertaken to identify the minor phases and to study the microstructural changes occurring in one of the more complex commercial alloys as a result of aging in the service temperature range, with particular emphasis on investigating the role of the ?' -phase. The microstructural changes were studied by electron microscopy and the minor phases were identified by X-ray and electron diffraction. MATERIALS AND METHODS Inconel-X alloy was selected for this investigation because the previous studies of Frey, Freeman, and white6 provided extensive information on the variations in metallurgical properties of this alloy resulting from high-temperature aging treatments. Specimens aged 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F were made available for the present use. These were taken from 1-in. round-bar stock of a commercial heat having the following weight composition: 0.04 C, 0.56 Mn, 6.59 Fe, 0.007 S, 0.38 Si, 0.03 Cu, 73.22 Ni, 14.97 Cr, 0.78 Al, 2.38 Ti, and 1-02 Nb. They were solutjon-treated at 2050 for 4 hr and then water-quenched prior to aging. Powder X-ray diffraction patterns were obtained from insoluble minor phases which were separated from the alloys by digestion in the reagent of Mahla and Nielsen.6 Back-reflection patterns were obtained from electrolytically polished surfaces of the bulk search to detect the ?'-phase' Cu-K a radiation was used in both cases. In the electron-diffraction studies, the general method developed by Heidenreich, Sturkey, and

Jan 1, 1959

By Henry Howe

- §1. INTRODUCTION.-Any given piece of metal is made up of a very great number of grains, usually microscopic, each of which is a perfect crystal save only in outward form, with cleavage planes of low cohesion, geometrically arranged quite as in the familiar non-metallic crystals. The plastic deformation of such a mass occurs chiefly through the slipping of the crystalline blocks of which each grain is composed along these cleavage planes, causing steps called slip bands to form on a previously polished surface. In this slip, the metal immediately adjoining each of the cleavage planes along which the slip takes place is thought to pass extremely rapidly through a very mobile state into the amorphous state, in which it is harder than the remaining still crystalline metal between the amorphous layers thus formed along the slip planes. Whether the slip planes below the surface in ferrite can be detected by cutting, polishing, and etching sections is in dispute; but if this detection is possible at all, it is usually made impossible by heating the metal even gently. In short, the change along the slip planes does not persist through heating, and it is thought not to persist through time even at the room temperature, nearly all the amorphous metal re-crystallizing. The network in Fig. 22 and the parallel N.-70°-E. lines in Fig. 21 are slip bands in copper.

Jan 3, 1915

By H. D. Williams, R. A. Scriven

The distribution of elevation angle of finite plane facets distributed symmetrically about a given axis is derived in terms of the angular distribution of lines which these facets produce in a plane section parallel to the axis. It is assumed that the facets are not markedly elongated in preferential directions. The theory is intended for application to the angular distribution in polycrystalline metals of slip planes and of particular grain boundaries on which certain phenomena such as cavitation can occuv. Illustrative examples are given in closed form and simple numerical techniques are de-ueloped for practical application. The results are applied to the distribution of cavitated boundaries in a copper specimen after fatigue at 400°C and it is found that voids form on the boundaries that exper~enced maximum shear stress. When investigating the distribution of elevation angle between a given axis and planes symmetrically distributed about this axis the angular distribution observed in a plane section parallel to the axis is not necessarily the same as the required distribution. Consequently a technique for processing the results obtained by sectioning methods is required. An example where such a technique would find application is in the problem of intercrystalline void formation during uniaxial tensile creep. Two theories have been proposed to explain this cavitation in terms of the normal and the shear components of stress, respectively. Hull and Rimmer (1959) postulate that the growth of intercrystalline voids is controlled by the rate of supply of vacancies from the grain boundary, the local vacancy concentration being proportional to the normal stress on the boundary. Gifkins (1956) considers that slip arising within a grain causes a ledge to be formed at the grain boundary which is subsequently opened up into a cavity by grain boundary sliding. It might be possible to differentiate between these mechanisms by determining the angular distribution of grain boundaries containing cavities since the former theory predicts a predominance of cavitated facets normal to the stress direction whereas the latter should favor an angle of 45 deg to this direction. In a similar manner an indication may be obtained of the type of mechanism responsible for intercrystalline cavitation during high-temperature fatigue. Davies and Wilshire (1962) have analyzed the slip-plane distribution in a nickel specimen but the problem was not treated in any detail nor was any account taken of the finite extent of the planes being sectioned. Hilliard (1962) has given a very general account of how anisotropy in the microstruciure can be related to measurements taken in one or more plane sections by expressing both the measured and the true angular distributions as expansions in spherical harmonics.* The present analysis is con-

Jan 1, 1965

By Nicholas J. Grant, A. W. Mullendore, Paul Predecki

The Duwez technique of splat cooling in which a molten droplet of metal is accelerated and made to impact on a cold, highly conducting substrate was investigated.- An apparatus for producing "splat" was constructed employing an explosive powder charge to accelerate the molten metal. Transport of the molten metal just prior to impact with the substrate was studied by means of high-speed photography. The molten particles are small spherical droplets from about 1 to 50 µ diameter. The average cooling rates for aluminum, silver, and a gold alloy splatted on nickel substrates at room temperature were determined experimentally and were found to vary from 18 to 5 x 10' C per sec. The heat-transfer coeficients for pure aluminum and pure silver splats cooled on nickel substrates at room temperature were found to be 2.7 to 6.8 and 13.6 to 54.2 cal per sec sq cm 'C (2 to 5 x 104 and 1 to 4 x 18 Btu per hr sq ft OF), respectively. Solidification rates in pure aluminum and silver splats were calculated. "SPLAT cooling" is a term describing a technique for extremely rapid freezing and cooling of molten metals and alloys to room temperature or below. The technique was developed by Duwez et al.' in 1960, and after refinement2 consisted in transferring a few tenths of a gram of molten metal to near sonic velocity to strike a suitably placed cold copper surface. Upon impact, the metal spread into a thin nonuniform film called a splat, about 10-4 cm thick. The splat particles produced in this manner were thin enough in some areas to be suitable for transmission electron microscopy, without further treatment, and, together with X-ray data, yielded a variety of structures which would be classified as follows: 1) supersaturated solid solutions (increase in solubility limit), 2) metastable crystalline stoichiometric and non-stoichiometric intermediate phases ( in Au-20.5 at. pct Si and in Au-14 at. pct Sb, respectively), 3) amorphous alloys, 4) retained high-temperature phases, 5) alloys having equilibrium phases present, but with unusual, markedly altered structures. The crystalline phases present in splats were usually extremely fine-grained and had low dislocation densities. Present interest in splat cooling centers around a study of the unusual structures produced by the technique, their contribution to alloy theory, and the possibility of the development of new or unusual properties. In addition, the technique is being examined for the production of bulk quantities of new high-strength alloys for low- and high-temperature use. Although a number of alloy systems have already been investigated by the technique, relatively little is known about the mechanism of splat formation and the physical conditions encountered by the metal during solidification and cooling. The purpose of this work was: 1) to determine the velocity, shape, and size of the molten metal droplets just prior to impact with the cold substrate; 2) to try to estimate or measure solidification rates, heat-transfer coefficients, and cooling rates in splats. EXPERIMENTAL TECHNIQUE Splatting Apparatus and Procedure. An apparatus similar to the type originated by Duwez et a1.,2 but employing an explosive charge to accelerate the molten metal, was used. A "Ramset" fastening tool (a gun normally used for driving studs into concrete, steel, and so forth) was mounted vertically above a resistance-heated graphite crucible as shown schematically in Fig. 1. A splat product was produced by melting a few tenths of a gram of metal at the position shown in Fig. 1, and then exploding a powder charge in the breach. The shock wave thus generated traveled down the barrel into the furnace, ejecting the molten metal through the 0.06-in.-diameter hole at the bottom of the crucible. The ejected metal was impacted on a high-conductivity metallic substrate where it formed a splat. High-Speed silhouette Photography. In order to investigate the size and shape of the ejected, molten metal just prior to impact with the cold substrate, high-speed silhouette photographs were taken, and are shown in Figs. 2 and 3. These photographs were obtained with the aid of an Edger-ton, Germeshausen, and Grier microflash unit and a submicrosecond flash drive equipped with a variable time delay. Two types of triggers were

Jan 1, 1965

By George S. Rice

The increasing use of mechanization at the face of the workings in coal mining and the consequent necessity of special supports of the roof has led, in several countries, to considerable scientific investigation, including physical tests in mines as well as on specimens of roof rocks to obtain data on the behavior of the immediate roof strata and on the effect of its pressure on supports while the coal is being mined. The investigations discussed in this paper do not include studies of the ultimate effect of subsidence and movement of the roof rock over the mine excavation, upon higher strata and the surface, but are confined to the immediate underground effects in the workings. The more recent principal investigations which have been brought to the attention of the writer are as follows: Germany.—The trial of strip packing, the usual method employed in Great Britain in longwall workings, as compared with complete packing heretofore used in Germany and in France to minimize subsidence; the behavior and strength of metal props under load; the testing of the strength of coal measure rocks, in the laboratory of the Technical High School of Breslau; and an investigation, by a special commission, concerning "bumps" as a possible cause of instantaneous outbursts of gas in coal mines of Lower Silesia. France.—The cause of instantaneous outbursts of gas in the Gard mines and tests by the official French experimental organization of the "electrical resistivity" of coal as a possible means of detecting a condition preceding an instantaneous outburst. Great Britain.—The subsidence of the roof and rise of the floor preceding and during excavation of the coal, in longwall and in room-and-pillar or bord-and-pillar workings; the compression and lateral movement of the road packs in longwall back from the face; the extent of separation of the immediate roof layers from the higher strata following mining excavation;

Jan 1, 1932

By J. R. Long, T. R. Graham

THIS report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. PRELIMINARY WORK In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, 0 to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening, effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By H. M. Chance

(Butte Meeting, August, 1913.) ADEQUATE treatment of the difficulties surrounding the valuation of mineral lands requires that agreement be first reached defining value as understood for the purpose of appraisal. To define value as the price of a product is not sufficient, and does not assist us in using the factors that cause variations in values and in relative values. The real value of any product depends primarily upon its relation to the necessities, comforts and pleasures of mankind. As the necessities, comforts and pleasures of the civilized races differ-from those of more primitive man, the value of products varies with the degree of civilization and the environment of the consumer. Coal has no value to the savages of warm climates, and arrow-head flint none to the residents of New York. It has long been recognized that what has. been termed ?intrinsic value " must be limited to materials that are essential to existence-air, water, food. But " intrinsic value " cannot be measured in monetary terms. The intrinsic value of a bushel of wheat is due to the fact that it will support the life of an individual for a certain definite time, but this fact does not enable us to measure or to express that value in monetary terms. It has often been proposed to adopt as a measure of the value of any product the quantity of labor necessary to produce it, but this method is of limited application, and will not apply to what may be termed " intrinsic values." For many reasons it might be well, while assenting to the fact that any material may be intrinsically valuable, to abandon the use of the term "intrinsic value." One of these reasons is the tendency to confuse the idea of " intrinsic value with a value that is conferred by economic conditions, that is purely artificial and that may be permanent or evanescent. Intrinsic value must from its nature be permanent and unchangeable.

Jan 7, 1913

By F. P. Dewey

The most serious problem that confronts the lead-smelter is the waste caused during smelting by the volatilization of both lead and silver, which are consequently lost in the form of fume. It is not difficult to collect a portion of the solid materials passing out of the

Jan 1, 1890

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969

By Norman Pilling

The micrographic analysis of silicon steels is possible if a dilute solution of nitric acid and methyl alcohol in nitrobenzol is used. The action of this reagent differs from that of sodium picrate in that there is no persistent deep-seated staining and the solution is used cold. THE technical difficulties hampering the metallographic analysis of silicon steels are chiefly the result of the extreme corrodibility of these alloys. The addition of silicon to iron in increasing quantities, up to about 6 per cent., rapidly increases the susceptibility of the alloy to chemical attack, not only in acid solution, but in water. This renders the preparation of metallographic sections very difficult, because of a non-selective attack upon the finely polished surface by the water used as a lubricant in polishing. This water attack masks the true structural details revealed by suitable etching reagents. It is thus necessary to use alcohol as a polishing lubricant in the last stages of preparation and to avoid all etching reagents having an aqueous base. A specific reagent for the identification of iron carbide in ferrous alloys, and the one hitherto used almost exclusively by metallurgists, is an alkaline aqueous solution of sodium picrate, which stains this constituent selectively. Its application to silicon steels has not proved successful, as its distinctive selective action is more or less completely hidden by the general attack of the aqueous solvent on the silico-ferrite, greatly accentuated by the fact that this reagent must be used at its boiling temperature (105° C.). Thus, a powerful metallographic aid to the study of the higher silicon alloys, such as transformer steels, is lost. A new reagent has been developed for the purpose of overcoming this difficulty. It is with some hesitation that the list of etching reagents, already overburdened, is increased, but the properties of this new reagent are advantageous in several ways and a definite field for it may be found in the metallography of ferrous alloys.

Jan 1, 1924

By R. W. Heckel

The growth and shrinkage rates of second-phase particles of various size distributions are analyzed in terms of five mathematical models. These models apply to various forms of diffusion-controlled growth (one model) and interjace-controlled growth (four models). The expression for diffusion-controlled growth assumes local equilibrium at the interface between the second Phase and the matrix and through the choice of the proper flux area perrnits the definition of minimum diffusion-controlled growth kinetics. The interface-controlled kinetics models consider the situations where the rate-controlling step occurs at either the interlace undergoing solution or the interface undergoing deposition. In addition, each of these interface-controlled kinetics models is analyzed for interface reaction rates which are independent of the thermodynamic activity gradient across the interface or proportional to the gradient. THE variation of the size distribution of second-phase particles in a solute-saturated matrix has been a stimulating topic for many years. Research has been carried out in this area for situations where the matrix was either liquid or solid. It is well-understood that the over-all process results in an increase in the average particle size, a decrease in the total number of particles per unit volume, and a net decrease in surface area. Greenwood1 has presented a mathematical model based upon the mass balance existing between growing and shrinking particles. His analysis is stated in terms of Fick's First Law using concentration gradients set up between particles of different size as a result of the effect of surface curvature on solubility. Greenwood's analysis indicates that the mean particle size should increase approximately as the cube root of time. Asimow2 has shown that several of the simplifying assumptions employed by Greenwood may be eliminated from this diffusion-controlled model with little increase in complexity. Lifshits and Slyozov3-5 have also considered the growth-shrinkage problem involving diffusion-controlled kinetics. Their analysis was extended to include the effects of interacting particles ("kinetic approximation"), particle shape, and elastic strains. These authors also show that the mean particle size varies as the cube root of the reaction time. wagner6 has formulated expressions for both diffusion-controlled kinetics and interface-controlled kinetics in the growth-shrinkage problem. Wagner's diffusion-controlled kinetics is based upon the same form of mass balance using Fick's First Law as used by others and is shown to be applicable to situations where kr >> D (k is the interface reaction constant, r is the particle radius, and D is the diffusion coefficient). This analysis also yields a mean particle size which varies as the cube root of time, in agreement with other workers. Wagner also developed interface-controlled kinetics to handle kr « D. This model was based upon the fact that the interface reaction rate is proportional to the interface area. Wagner assumed that the rate was also proportional to the thermodynamic activity difference, ?a, existing across the interface. Thus, the specific reaction rate at the surface of radius r was defined as k • 4nr2 . ?a. It is the purpose of the present paper to reconsider the processes of diffusion-controlled growth and interface-controlled growth in the variation of particle-size distributions as a function of time at constant second-phase volume. The analyses are formulated in a manner which permits data obtained

Jan 1, 1965

By Parke A. Hodges

CHROMIUM, one of the most vital of the strategic metals, has constantly increasing importance as research expands potential uses in alloy steel metallurgy. All signs point to a steadily growing use for chrome ore, and the general subject has received a great deal of attention recently.1 A relatively little known country, Southern Rhodesia produced a total of 5.949 million tons, or 18.6 pct of the total world chrome output, between 1906 and 1950, according to figures from the U. S. Dept. of Commerce. According to U. S. Bureau of Mines figures, Southern Rhodesia produced 291,525 tons in 1950 and 300,267 tons in 1951, or approximately 13 and 11 pct, respectively, of world production for the two years. In 1953 the Rhodesian Vanadium Corp. produced about 85,000 tons of which probably 7,000 tons were concentrate. Production by other companies was high. Large in themselves, the figures assume even greater significance because most of this output is of metallurgical grade.

Jan 8, 1954