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HARD as it is at any time to provide more than three million tons of coal each year for power plants, the task really gets rugged in the wintertime when the fuel freezes solid in the cars. At the Marysville plant of the Detroit Edison Co. the problem of unloading cars of frozen coal was severe because there was an unloader over only one of the two tracks in the coal unloading house. Moving downward by their own weight, with no driving force to aid them, the spuds of this old unloader were unable to break through the crust on a frozen coal car. 20,000 Lb Force To meet this problem, a new mechanical car unloader was installed over No. 2 track and placed in service in December 1947. It is a Kenney type unloader built by Heyl & Patterson, Inc. of Pittsburgh, Pa., a modification of equipment originally designed to unload iron ore cars. The major advantage of this unloader is the force with which it can drive the sharp spade on the end of its ram down through the pockets of a frozen coal car. The unloader consists of the following major units: 1. A traveling bridge structure. 2. A traveling trolley. 3. A retractable and oscillating ram. 4. The operators cab and controls. The bridge is provided with safety hooks to prevent its being lifted from the rails by the upwards push of the ram. The bridge will travel 190 fpm and has sufficient traction on its four wheels to move three loaded 70 ton cars. The trolley runs on tracks supported by the bridge girders and also has upper tracks to control the push from the ram. Two of the single-flange trolley wheels are driven by a one and a quarter hp dc motors equipped with magnetic brakes. The ram is raised and lowered by a 20 hp dc motor equipped with a magnetic brake. A full stroke of a little over 14 ft is given the ram through its rack and pinion drive and the spade can be pushed down into a loaded car with a force of about 20,000 lb. A 15 hp dc motor with a magnetic brake is applied to this drive and is able to swing the ram 45º either side of the vertical. The usual procedure in emptying a coal car is first to drive the sharp spade down through the coal until the pocket is opened and the coal starts to run out the hopper. When all the hoppers are open, the sweeping action of the ram and spade is used to move the remainder of the coal in the car over to the open hoppers. The travel of the trolley permits cleaning the sides of a coal car with the edges of the spade, using the sweeping motion of the ram. It is still necessary to clean out the corners of the car by hand. Final Clean-Out This unloader was a new development and there were improvements to be made before it was completely satisfactory, such as reduction in speed and conversion to ac drive motors. However, it helped at Marysville and unloaded many frozen cars that would have taken a lot of heating to thaw out enough for the old unloader to handle. The mechanical coal unloader described above was a considerable improvement but still left a job to be done by hand-the final cleaning out of the coal cars. The ram had the ability to open a hole through the hopper cars, but did not meet required unloading speed. To eliminate hand cleaning a car shakeout, manufactured by Hewitt Robins, Inc. was added to the installation. This equipment is used to clean the coal car out after the unloader has provided an

Jan 1, 1952

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By T. M. Kegley, J. H. Frye, D. L. McElroy, M. L. Picklesimer, E. E. Stansbury

Measurements of rate of growth, thermodymmic quantities, and partitioning of Mn are reported for high-purity eutectoid Fe-C and Fe-C-Mn steels for the auistenite-pearlite reaction. Evaluztion of the cotnstants of a derived-rate equation with these data indicate that Mn additions cause the decrease observed by increasivg the activation energy and apparent activation entropy or the movenment of complexes at the interface. A diffusion-controlled mechanism is not required. Appreciable partitioning of Mn to cementite occurs entirely behind the austenite-pearlite interface for more than 30°C of subcooling. ThE growth of pearlite from austenite has been extensively studied over a period of years. but the rate-controlling step in the process is not known nor is the mechanisrn of the effect of alloying elements understood. A comprehensive review of the subject has been given by Mehl and Hagel. The present study has been concerned with further considerations of the effects of alloying elements on the rate of growth of pearlite. Analytical relatioriships for the rate of growth of pearlite have been considered by Zener.2 Turnbull,3 Machlin,4 Cahn.5 Frye,6 and Frye et a1.7 The derived expressions in each case involve the free energy of the transformation. the interlamellar spacing. and some rate term of the nature of the diffusion coefficient. mobility or frequency of occurrence of some rate-determining step. The treatments. of course. differ in detail. Further consideration is given in the present paper to the equation of Frye, Stansbury. and McElroy which was derived from modified absolute rate theory without in any way specifying the mechanism of the reaction. This equation is r=c ? T ? F exp -?E*/RT [1] where r = rate of growth in mm/sec c = a constant AT = equilibrium transformation temperature minus actual transformation temperature "C ?F = free energy per mol of austenite minus that of pearlite ?E* = activation energy R= gas constant ?F in Eq. [1] is computed from the following: ?F=?H?T/To - ?T' dT' ?T' ?CdT"/T" [2] To To where AH is the enthalpy per mol of austenite minus that of pearlite at the equilibrium temperature, To, and AC is the difference in specific heat between austenite and pearlite per mol. Subsequently, Darken, Fisher, and Galligan8 have reported that a layer of ferrite separates pearlite from austenite at the growing interface (i,e., the advancing face of Fe3C is in contact with ferrite, not austenite) and the ratio of the thickness of this layer to the spacing of the pearlite has not been found to vary with alloy content or transformation temperature. This observation does not require any alteration in the above equation: however, it may require that a different significance be attached to the factor, AT. The AT term appears in Eq. [I] as a consequence of a factor for the amount of growth per complex transformed at the interface.* It is based *This is not the sole reason for expecting such a relationship. See Ref. 7._______________________________________________________ on a l/2 ?T dependence of the interlamellar spacing. Zener2 has developed a theory which leads to Soa 1/?V where So = the pearlite interlamellar spacing. This relation is as consistent with the data on interlamellar spacing as other relationships, although, as pointed out by Mehl and Hagel,1 the data are not sufficiently precise to consider the relationship as confirmed. The work of Darken, Fisher, and Galligan8 requires that the above be written where f = the thickness of ferrite layer between austenite and pearlite. The present paper is concerned with iron-carbon-manganese eutectoid alloys and reports experimental measurements of the following kinds: 1) the effect of

Jan 1, 1961

By AIME

TURMOIL has been rampant in the lead producing industry during 1946. The chronic labor shortage was aggravated by various work stoppages in mines, smelters, and refineries, while shortage of materials was widespread. Price uncertainties helped to confuse the situation in many countries and particularly in the United States until the removal of price control in the latter part of the year. At the end of the first year of peace, lead, which had been comparatively plentiful during the war years, was a scarce and high-priced metal throughout the world. It is the hope of the industry that the law of supply and demand, if allowed to operate without interference, will bring about a satisfactory balance between production and consumption. Under these circumstances it is not surprising that there have been few important developments in the metallurgy of lead, though a number of items of general interest to the industry have been reported. An ore body which may prove to be of considerable importance has been discovered at Mpanda, Tanganyika. The scarcity of lead ore is illustrated by the announced reopening of the La Manche lead mine in Newfoundland, idle for 56 years. A new lead producer came into production when Rhodesia Broken Hill started up its new smelter. Lead concentrate of 75 per cent grade is smelted in Scotch hearths and the lead is refined to market grade by the Harris process without desilverizing. Production is about 1000 tons per month. One Australian lead producer, Mount Isa, has returned to lead production after having operated its lead plant for the production of copper during the war. The East Chicago plant of the International Smelting and Refining Co. has been sold to the Eagle-Picher Co.

Jan 1, 1947

By J. F. Held

In a study of the influence of cold rolling on mechani cal properties of steel, it was found that the specific rolling procedure influenced crystallographic orientation. Properties developed by several rolling modes were determined and related to crystallographic orientation. Sanzples were cold-rolled various amounts on a laboratory mill. When palm oil was used as a lubricant, the crystallographic orientation was homogeneous throughout the thickness of the samples. Other samples were rolled without lubrication. Variations in intensity of the recrystallization texture components persisted throughout more than 50 pct of the volume of these samples. When the average plastic strain ratio, which is dependent upon crystallogvaphic orientation, was plotted as a function of percent reduction, a maximum was found at 40 pct in the samples which contained the observed texture variation. No maximum was found for the samples with the homogeneous texture distribution. Other mechanical properties, such as tensile strength and yield strength, were not influenced by the variation in crystallopaphic orientation. MECHANICAL properties of steel sheets depend, in general, upon the structural properties of the steel. For example, the Petch equation describes the relationship between yield strength and grain size. Other properties, such as hardness, vary with chemical composition. The plastic strain ratio, or R value, has been found to be dependent upon crystallographic orientation . In the course of investigating the effect of cold rolling on mechanical properties, it was found that a previously reported relationship between percent cold reduction and R value was not always observed. Published data had shown that the optimum cold reduction for best R values is 70 pct for aluminum killed steel.' However, by altering the rolling conditions, the optimum reduction can be shifted to much lower values, or it can be moved to very high values. This paper describes the rolling conditions that lead to shifting of the optimum cold reduction. The effect of rolling conditions on the various structure parameters and the resulting mechanical properties are evaluated. EXPERIMENTAL PROCEDURE Samples of three low-carbon aluminum killed steels were cold-rolled various amounts on a 9-in.-diam 2-high laboratory mill. Hot-mill thermal practice and steel chemistries are listed in Table I. Steel A was rolled with palm oil lubrication and heavy reductions on each pass; i.e., a total reduction of 75 pct was ac- complished with a maximum of five passes. Steel B was rolled without lubrication, and light reductions were given on each pass. After approximately 75 pct reduction, it was necessary to use a small amount of light oil to achieve any additional reduction in thickness. Following cold reduction, the samples were box-annealed at 1300°F for 10 hr. The heating rate between 800" and 1300°F was 50°F per hr, and the cooling rate following the soak period was 50°F per hr. Tensile specimens were machined from the annealed material and these were used to measure yield strength, tensile strength, and the plastic strain ratio (R value). Recrystallization textures were determined by an inverse pole figure technique.*'3 Integrated intensities of the (110), (002), (112), and (222) reflections were recorded for those planes lying parallel to the sheet surface. Examinations were made on both surfaces of each sample, and also at various levels beneath each surface to approximately 0.010 in. depth by etching techniques. RESULTS R Values. The R values obtained in steels A and B are shown as a function of percent cold reduction in Fig. 1. No optimum cold reduction was observed in steel A, rolled with palm oil lubrication. It is likely, however, that an optimum reduction would have occurred had higher reductions than 88 pct been employed. The optimum reduction in steel B occurred at 40 pct. The behavior in both of these steels is quite

Jan 1, 1968

By Richard D. Divine

In the Parkes process of extracting precious metals from lead, zinc is added to the molten lead containing gold, silver, copper, and some antimony. These metals, with the exception of antimony, form an alloy with the zinc by reason of their greater affinity for it than for the lead, and this alloy, being lighter than lead, rises to the top, carrying the precious metals with it, whence it can be removed by skimming. These skimmings are further treated for the separation of the zinc therefrom, and the recovery of the precious metals, the zinc being driven off by heat and again used for another operation. In addition to the zinc that combines with the silver, etc., a certain amount is necessary to saturate the lead, and it is therefore necessary to treat the desilverized lead to free it from this residual zinc. TO do this it is heated again in a reverberatory furnace and air or steam is blown through it. This oxidizes the zinc together with a small amount of lead and antimony, leaving the lead free from zinc and antimony, and forming oxides of these metals, which rise to the top and are skimmed off. This process relates to the separation of the metals in these oxides or skimmings. The skimmings are cooled, crushed, and mixed with carbonate of soda and pulverized oil coke. The mixture is heated in a reverberatory furnace on a bath of lead, to about 1,000" C. The metals are reduced by the coke, the lead and antimony go into the lead bath, while the zinc is volatilized and burned to oxide. This impure oxide is at the present time treated at Omaha by the Hall process of electrical precipitation, making a very pure metallic zinc. It can also be very easily refined by the old Schnabel process of using ammonia and carbon dioxide as a solvent. It seems to be in an ideal form for this purpose, and very few changes from the original method are required to obtain the zinc oxide practically C. P., leaving the lead and antimony as residues. There has been considerable difference of opinion regarding the effect

Jan 1, 1915

By Richard Divine

IN the Parkes process of extracting precious metals from lead, zinc is added to the molten lead containing gold, silver, copper, and, some antimony. These metals, with the exception of antimony, form an alloy with the zinc by reason of their greater affinity for it than for the lead, and this alloy, being lighter than lead, rises to the top, carrying the precious metals with it, whence it can be removed by skimming. These skimmings are further treated for the separation of the zinc therefrom, and the recovery of the precious metals, the zinc being driven off by heat and again used for another operation. In addition to the zinc that combines with the silver, etc., a certain amount is necessary to saturate the lead, and it is therefore necessary to treat the desilverized lead to free it from this residual zinc. To do this it is heated again in a reverberatory furnace and air or steam is blown through it. This oxidizes the zinc together with a small amount of lead and antimony, leaving the lead free from zinc and antimony, and forming oxides of these metals, which rise to the. top and are skimmed off. This process relates to the separation of the metals in these oxides or skimmings. The skimmings are cooled, crushed, and mixed with carbonate of soda and pulverized oil coke. The mixture is heated in a reverberatory furnace on a bath of lead, to about 1,000°C. The metals are reduced by the coke, the lead and antimony go into the lead bath, while the zinc is volatilized and burned to oxide. This impure oxide is at the present time treated at Omaha by the Hall process of electrical precipitation, making a very pure metallic zinc. It can also be very easily refined by the old Schnabel process of using ammonia and carbon dioxide as a solvent. It seen-is to be in an ideal form for this purpose, and very few changes from the original method are required to obtain the zinc oxide practically C. P., leaving the lead and antimony as residues.

Jan 8, 1914

By R. A. Wagstaff

The method of charging a reverberatory furnace has changed many times since smelting was introduced in this country from the old smelters of Swansea, England. The cause of the latest change at the Garfield plant has been the excessive fineness of the charge due to fine grinding in the concentration of the crude copper ores. The many desirable features of deep-bath smelting as now used at Garfield have been proved. The old method of dropping the charge through holes in the arch (known as center-feed method) causes excessive dusting which makes heavy slag and flue-dust losses, also rapid deterioration of the silica brickwork of the furnace through fusion with the iron oxides from the dust. The purpose of this paper is to describe a gun feeder that was designed to overcome the disadvantages of the older methods of center feeding and still maintain the good features of deep-bath smelting with the hot finer charge. A gun feeder was designed to introduce the finely divided hot calcines under the moving gas stream of the combustion zone and still have them spread in a uniform blanket over the highly heated matte bath. The temperature of the furnace was so great that it was impossible to maintain a stationary feeder, so a movable feeder was designed that could be introduced into the highly heated zone and be withdrawn after the charge had been dropped. It was necessary to protect the nozzle of the gun with a water-cooled coil. Many different types of protected nozzles were tried, such as air jackets, water jackets and heat-resisting steel alloys, but none proved satisfactory. The angle of inclination of the feeder was found to be an important factor in spreading the charge evenly over the surface of the bath. An angle of 34" to 37" was found to be the most advantageous. To allow a continuous flow of ore from the charge car to the point of discharge inside the furnace, the feeder was made with telescopic connections. The pipe leading from the car is stationary and forms the inside part of the telescope. The outside section of the telescope is movable, and is

Jan 1, 1934

By C. S. Sivil

To modern civilization the platinum metals are of inestimable value. Their distinctive properties, both physical and chemical, render them indispensable in an age in which the processes of the laboratory are becoming an essential part of the daily life of the world. Generally, their function, though vital to particular processes, is not spectacular, and so remains unknown to all except the operators. Early Methods of Manufacture The properties of platinum were recognized as of prime importance for scientific work at a very early date, probably between 1750 and 1760. The difficulty of making articles from it seemed almost insurmountable, because no means of attaining the temperature necessary to melt it were known at that time. It is true that solid platinum could be obtained by fusing the metal with a more volatile metal such as arsenic, which was subsequently driven off by baking, but such a method, at its best, would give only a very brittle product, which was totally unsuitable for the purposes for which it was intended. Little, if any, progress could be made until it was discovered that platinum sponge, heated to white heat and hammered in an iron or clay mold, would metallize and retain the shape of the mold. This was a process that could not be wholly satisfactory but from it developed the method of pressing the sponge in a mold and forging it at white heat into wire or sheet. At present a somewhat similar process must be used for fabricating articles of tungsten, molybdenum and other metals of high fusing point, as with these metals we face today the same problems that the scientists of the eighteenth century encountered with platinum, but possibly the next significant advance in the metallurgy of these metals will be the devising of means to melt and cast them. TO some extent this method of preparing platinum has survived, particularly in Europe. There are one or two objections to it, but they are not serious, as they can be surmounted with proper precautions. In the first place, the material is spongy and its millions of cavities contain entrapped air. Unless this is removed by thorough forging above 1000" C. the resultant sheet shows blisters. To give such a thorough forging,

Jan 1, 1931

Discussion of the paper of F. C. LANGENBERG and R. G. WEBBER, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 291 to 300. HENRY M. HOWE, Bedford Hills, N. Y.-The results here given are of great interest and are welcome as forming another rivet to increase the stability of our present theories of the constitution and properties of steel. The important discovery is that the hysteresis increases with the fineness of the structure, that is to say with the extent of contact between the particles of ferrite and cementite. All of the specimens except No. 4 consist of ferrite and cementite of different degrees of intimacy of admixture. If hysteresis represents something akin to surface friction, which retards the rotation of the ferrite on the application and release of the magnetizing force, then it is only natural that it should increase as it does with the intimacy of admixture, because it is at the surface of contact of a given particle of ferrite with the neighboring particles of cementite that this friction is to be expected, and of course the extent of surface must in¬crease with the intimacy of admixture. The somewhat greater hardness of specimen 4 than of the others may perhaps he referred to the principle discussed in my paper, Why Does Lag Increase with the Temperature from Which Cooling Starts?' The furnace-cooled specimens were cooled so slowly that the influence of the initial temperature of heating is effaced. But in the air-cooled specimens we have the suggestion that the high temperature, 1,000°, from which the cooling of No. 4 started has prevented the completion of the transformation, with the result that the metal is slightly harder than any of the others. The difference is not to be explained by difference in the fineness of structure, because the whole range of fineness from No. 1 to No. 6 is accompanied by no change in hardness, the only change being an appreciable increase of hardness following the air cooling from 1,000°.

Jan 5, 1915

By F. R. Hensel

P. R. Kalischer.*—I should like to amplify a little one of the points made by Dr. Hensel, and rather violently disagree with him at the same time. He brought out the point that when the higher forming pressures are used on the green compacts there is a marked decrease in the density as sintered. We found that to be true and, of course, many of you notice that that is true with copper compacts also. But, in my opinion at least, it is not true that the expansion is due to entrapped air. We have vacuum-pressed both silver and copper compacts and obtained almost exactly the same numerical expansion as we secured by pressing in air. The powder, however, that is vacuum-annealed does show a slight decrease in expansion on sintering, but almost the entire increase on expansion can be overcome by very slow rates of heating. And it is our opinion that a majority of the expansion is due to dissolved oxygen in the discrete metal particles themselves rather than to entrapped gases. Another interesting observation that we have made is that often with silver or copper compacts it is desirable to silver solder or braze the compact into some part of a piece of equipment after completing powder metallurgical operations on it. If such a compact is sintered and coined, say a silver compact, given an initial forming pressure of 10 to 15 tons per square inch, and sintered, there is an adequate amount of shrinkage and it can be coined at about 50 or 60 tons per square inch and bring up the density nearly to theoretical. If, then, that compact is silver-soldered into some part of a fixture or a machine, it will expand very beautifully, and the only way that this can be overcome. as far as we know, has been to reanneal after the coining operation at a temperature higher than is to be used in any subsequent operation. In that way, a density very nearly theoretical can be achieved, but the coining operation cannot be carried to the excessively high pressures or expansion and bubbling of the compact will occur again.

Jan 1, 1945

By L. J. Trilli

RECENT studies have indicated that there may be considerable difference in the cleanliness of the central pipe cavity of open top ingots. It has been speculated that some of this difference arises becausk of reactions that occur during reheating in the blooming mill soaking pits. In this respect, it has been recognized that an oxide coating or flow of slaggy material in the cavity could inhibit welding during hot rolling and thus reduce the amount of sound product which may be obtained. This note is intended to summarize some observations on the structure of a split ingot top which may be useful in describing a mechanism whereby the shrinkage cavity could be oxidized during reheating. A 221/2x241/2 in., big-end-down, test ingot was secured from a routine production heat. The chemical analysis representing this ingot is as follows: 0.08 pct C, 1.04 pct Mn, 0.062 pct P, 0.315 pct S, and 0.02 pct Si. The deoxidation practice used on the heat from which the experimental ingot was

Jan 1, 1957

By Tasuku Fuwa, John Chipman

Equilibrium data on the reactions of gases with carbon and oxygen dissolved in liquid iron are reviewed and correlated. A source of error in oxygen analysis of graphitic samples is exposed. New experimental data on the oxygen content of high -carbon iron in equilibrium with carbon monoxide indicate that the activity coefficient of oxygen is decreased by additions of carbon. The carbon-oxygen product decreases slightly with increasing carbon content. In recent years a number of investigations have been reported dealing with the equilibria between carbon and oxygen in liquid iron and gases containing carbon oxides. The laboratory study of these reactions dates back to 1931 with the publication of a paper by Vacher and Hamilton' on "The Carbon-Oxygen Equilibrium in Liquid Iron". The principal object of this study was to obtain data on the reaction shown by Eq. [3] below; their data and others by vacherZ permit evaluation of the other equilibrium constants as well. Subsequent studies have been reported by Matoba, Phragmen and Kalling and by Marshall and Chipman.5 The equilibria may be expressed by the following three equations: C + CO,= 2CO;Kl = Pc° [1] 0-+CO = CO,;K2=-P co, "0.PCO c + O = CO; K3 = In the equilibrium constants, ac and a0 are taken as equal to [% C] and [% 0] respectively in the infinitely dilute solution. At finite concentrations an activity coefficient is introduced such that ac =fc [%C], and so forth. It is to be noted that these equations represent only two independent relations, the third being derivable from any two. Richardson and Dennis have determined the conditions of equilibrium in reaction [I] at temperatures of 1560" to 1760°C. Their results have been confirmed by Rist and chipman7 who have shown how the data may be extended to cover the entire range of liquid compositions at temperatures from the eutectic up to 1760°C. An approximate confirmation has been reported by Fuwa and chipman.' These investigations also established the activity coefficient of carbon which was shown to increase rather rapidly with increasing concentration. For the very dilute solutions the value of Kl is expressed in the equation: log^i = - 7280/T+ 6.65 This equation leads to a value of Kl = 430 at 1540° C in excellent agreement with the average value of Marshall and Chipman.5 It is shown as line 1 in Fig. 1 together with the experimental observations. In the case of reaction [2] the direct experimental results can be supplemented by observations on the corresponding reaction with hydrogen, namely reaction [4]:

Jan 1, 1961

By Bernard G. Carbajal

The dielectric properties and thermal stability of glow-discharge polytnerized films of styrene, chloro-benzene, and other organics and photoresist filrns are presented. Variations in the glow-discharge polymerization procedure are related to thermal stability. Thermal treatwzents to improve the dielectric properties of both positive (A2 340) and negative (KMER) photoresists are given. THIS study of the dielectric properties of thin organic polymer films is part of a program to investigate the electronic applications of organic materials. Thin organic polymer films have been produced in an ac glow discharge,13 with a low-energy electron-beam process,4 and in an rf dicharge. A process has been developed during the course of this program for forming thin organic polymer films in a dc glow discharge. These glow-discharge polymerized (GDP) films exhibit some useful dielectric and insulative properties. Variations in the properties of the GDP films can be induced by changes in the source material (monomer) andor in the conditions of the glow discharge. Thin organic polymer films can also be produced from typical positive and negative photoresists. Some variations in the properties of the photoresist films can be induced by suitable post-application treatments such as thermal crosslinking. The properties of interest in this study are dielectric constant, dielectric strength, resistivity, and thermal stability. POLYMER FILM PREPARATION I) GDP Films. The GDP films were prepared in a dc glow discharge in an atmosphere of organic monomer vapor. The details of the glow-discharge procedure have been presented previously.6 Briefly, under the influence of a dc glow discharge organic vapors can be polymerized in the vapor phase and the resultant polymer (GDP film) deposits on and in the vicinity of the cathode. Substrates placed behind a screen cathode can be uniformly coated over all exposed areas. Pattern definition can be achieved using normal mask stencil techniques. Table I presents the pertinent parameters in the preparation of GDP styrene. Conditions of Forrrzation of GDP Styrene. The rate of deposition for GDP films was monitored using a current-time integrator. The thickness of the deposited film for a given set of experimental conditions was a function of the current-time integral. The fifth row in Table I is a compilation of the deposition rate of GDP styrene films. Other organic monomers behave in a similar fashion. With the exception of the highly halogenated saturated hydrocarbons, all organics subjected to the conditions of the glow discharge form GDP films. 11) Photoresist Films. Photoresists are normally recognized to exist in two forms, a low molecular weight, soluble polymer form (A) and a high molecular weight, crosslinked insoluble form (B). Typical negative photoresists are applied in the low molecular weight form A and converted to the high molecular weight form B by the action of light. (Positive photoresists are applied in form B and converted to form A by the action of light.) Eastman Kodak Metal Etch Resist (KMER) has been chosen as a typical negative photoresist. Polymer film samples were prepared in the same configuration used for GDP films. The KMER was applied in the usual fashion using a 120°C drying step (infrared-lamp heating) and a 180°C post-bake. Care must be taken to completely remove the solvent in the drying step and to properly develop and postbake to exposed photoresist. If the photoresist film is not properly dried and postbaked, severe blistering and peeling will occur during subsequent elevated-temperature exposure. Thickness can be controlled by varying the viscosity of the form A photoresist and the spin rate at application. AZ 340 was chosen as a typical positive photore-

Jan 1, 1967

By Jesse Betterton

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

Jan 1, 1933

By Thomas Leonard Watson

Introduction,...... Historical Statement,....644 Geology of the District,....645 The Weisner Quartzite,....647 Topography,. .....653 Rock-Weathering,..... The OcheR-Deposits,.....655 Petrography of the Quartzite,..655 Associated Ore-Deposits,....657 Chemical Composition of the Ocher,. 658 Mode of Occurrence of the Ocher,..659 In the Fresh Rock,....660 In the Residual Clays,...661 Origin of the Ocher,....662 Economic Features,..... Methods of Mining,..... Preparation of the Ocher,...664 Uses,........ Introduction. Knowledge of the existence of yellow-ocher deposits in Bartow county, Georgia, dates back to the early mining of manganese- and iron-ores in the vicinity of Cartersville. Systematic mining of the ocher in this area really began, however, probably not longer than a decade back, although the date of its first working is as early as the year 1877. The district has been, for a number of years, one of the principal producers of yellow ocher in the United States; and at no period of its development have mining activities been greater and more successful than at present. Systematic field-study of the ocher- and manganese-deposits of Georgia was begun by me while I was a member of the

Jan 1, 1904

By Carl F. Cline, Richard R. Vandervoort, Willis L. Barmore

THE objective of this investigation was to determine the high-temperature plastic deformation behavior of stoichiometric uranium mononitride as a function of stress and temperature. Interest in the properties of this material stems from its potential use in high-temperature nuclear reactor systems. The creep of other refractory compounds containing uranium (e.g., U02, UC) has been studied by various investigators.1"4 Fassler et al.4 have studied the creep of UN in vacuum from 1100° to 1350°C at stresses of 6000 and 8000 psi. In the present work, the creep of stoichiometric UN was investigated from 1500° to 1800°C at stresses from 2000 to 5000 psi in a partial pressure of 200 mm of nitrogen. The specimens were prepared by hot isostatic pressing of UN powder into cylinders of $ in. diam by about 1 in. high. After pressing, the specimens were heat-treated in nitrogen at 1900°C for 50 hr. The densities of individual specimens were determined by the water displacement method. All specimens were theoretically dense, based on a value of 14.32 g per cu cm.5 Principal metallic impurities in ppm by weight were: Ca, 50; Cu, 5; Fe, 30; Mg, 5; Ni, 10; and Si, 20. Oxygen content was 400 ± 50 pprn and carbon content was 100 i25 ppm. The nitrogen content was 5.56 ±0.05 wt pct. The average grain size for five specimens, as determined by the intercept method, was 0.14 i 0.01 mm. One specimen had a grain size of 2.0 mm. This large grain size is an anomaly, since all specimens had the same chemical and thermal histories. Specimens of 1/4 in. diam by 1/2 in. high were creep-tested in compression in a clam shell furnace heated by W-25 pct Re sheet elements. Temperature was measured to ilODC by an optical pyrometer which had been calibrated by a standard source. The distance between fiducial marks on the specimen was measured before placement into the furnace. The furnace chamber was evacuated to 10-5 Torr and back-filled to 200 mm N2. After heating rapidly to temperature, the load was applied and controlled to ±2 pct by an Instron testing machine. Upon initial loading, the specimen was deformed until a constant crosshead rate was obtained, then quenched to room temperature, remeasured, and replaced in the furnace. Upon subsequent reloading at temperature, the crosshead rate was constant for the selected condition indicating steady-state creep.

Jan 1, 1969

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962

By J. M. Hodge, M. A. Orehoski

THE relationship between hardenability based on a 50 per cent martensite criterion, and that based on higher percentages of martensite in a number of low-alloy steels was discussed in a previous paper by the authors.1 It was found that the differences between the hardenability values based on the 50 per cent martensite and full martensite criterions increased as the hardenability increased and that, in the steels of higher hardenability, these differences were fairly large. Furthermore, it was found that these relationships could be expressed with reasonable accuracy as a function of the hardenability. The importance of the full martensite criterion of hardenability in relation to the attainment of the optimum mechanical properties of tempered martensite was emphasized in the earlier paper. The purpose of the present work is to study the effects of some of the individual alloying elements on hardenability, using three different percentages of martensite as criteria, and thereby to evaluate the role of these individual elements in the general hardenability relationships previously reported. EXPERIMENTAL PROCEDURE Induction-furnace heats weighing 17-lb., of the compositions given in Table I, were cast and forged into 1 ¼ in. round bars. All heats were killed with aluminum additions corresponding to 1 lb. per ton. The compositions were chosen to represent several series of steels, in which only one alloying element would vary and in which the nonmartensitic constituents on quenching would be predominantly bainitic. All bars were normalized from 1650°F. and tempered one hour at I 150°F. prior to the hardenability determinations. Hardenability values are based on metallographic examination of standard Jominy bars, quenched from 1600°F. (I hr. and 20 min. heating time). The general procedure was the same as outlined in detail in the previous paper; (I) that is, the distance from the quenched end of the bar to the point of 0.1 per cent transformation was first measured on the microscope and then the percentage of martensite was estimated at every 0.05 in. from the quenched end, and these percentage values plotted against the distance along the bar. In this case, samples 2 in. long were cut from the quenched end of the Jominy bars and 10 fields were examined and averaged at each distance. The conversion of Jominy distance to ideal diameter is based on a revised correlation curve (Fig. I). This curve is based on work carried out at the Research Department of the South Chicago Works, Carnegie-Illinois Steel Corporation, and represents a direct correlation between hardenability values as deter-

Jan 1, 1946

By H. H. Johnson, Eric W. Johnson

A newly developed ac technique was used to measure the electrical-resistivity changes associated with both cyclic stressing and subsequent annealing of high-purity and OFHC copper. The early stage of push-pull fatigue was explored at 293° and 4.2°K, with stresses chosen for an expected fatigue life of 2 to 8 X 105 cycles. For high-purity copper, fatigue at 293°K was accompanied by an initial increase in resistivity. After about 5000 stress cycles, no further increase was observed. Annealing studies showed that the resisticity increment could be accounted for solely in terms of an increased dislocation density, to about 2 x 1010 disl pev sq cm. Fov 42°K fatigue, however, the resistivity increased continually, with no evidence of saturation, as approximately (No. of stress cycles)1/4. This is intevpreted to result from both dislocation multiplication and vacancy production; estimated vacancy concentrations are 10-4 to 10-9. The continuous resistivity increase was inhibited by interspersed annealing treatments at 293°K, which also raised the level of the stress-strain curve. These effects are attributed to annealing of vacancies into dislocation loops. In contrast, OFHC copper fatigued at 4.2°K showed saturation of electrical vesistivity after only a few hundred cycles, and it appeared that vacancies annealed out completely between 77° and 293°K. MaNY observations suggest that both dislocation multiplication and point-defect production are important aspects of fatigue deformation. An increase in dislocation density with number of stress cycles has been demonstrated or implied by several experimental techniques, including optical metallography with lithium fluoride,&apos; electron microscopy with copper,2 thermal conductivity of Cu-Zn alloys,3 and peak-stress measurements during cycling at constant plastic strain amplitude.4,5 At low amplitudes and/or stresses saturation of fatigue hardening and dislocation density occurs early in the expected fatigue life,4-6 frequently by a few hundred cycles. The evidence for point-defect production is somewhat less extensive, but it is nonetheless persuasive. Rosenberg7 reported briefly that, for equal stresses, copper fatigued at liquid-hydrogen temperature displays an increase in electrical resistance some ten times that which accompanies unidirectional stressing. Further, the extra resistance saturates after a few hundred stress cycles, and does not anneal significantly until a temperature of about 170°K is attained.&apos; Point-defect production during fatigue is also suggested by 1) the softening during cyclic stressing of initially strain-hardened polycrystal-line copper9, 2) the strong temperature dependence of the yield strength of fatigue-hardened mono- and polycrystalline copper,579"0 and 3) the influence of intermediate annealing upon slip-band formation in copper fatigued at 90°K.8 It is evident that characterization of the fatigued state requires a knowledge of both point-defect and dislocation densities. For this purpose electrical-resistivity measurements are useful, but they are difficult to perform because of geometric limitations. Push-pull fatigue is necessary to obtain a macroscopic ally uniform deformation over the specimen cross section; however, the specimen must then have a low slenderness ratio to avoid plastic buckling, while the standard dc resistivity technique requires a very slender specimen for

Jan 1, 1965