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By L. A. Roe, John Jan

Iodine is a soft, lustrous, grayish-black nonmetallic element with a density of 4.9. It is the least active of the four members of the halogen family. The other members are, in order of increasing activity, bromine, chlorine, and fluorine. Iodine is a solid at ordinary temperatures, while bromine is a liquid and chlorine and fluorine are gases. Iodine melts at 113°C and volatilizes at 184.4°C to a blue-violet gas with an irritating odor. It occurs in nature only as iodates and iodides or other combined forms. It was discovered by Bernard Courtois in France in 1811, who noticed its presence as an unknown substance in crude soda ash obtained from burning seaweed. Gay-Lussac recognized it as a new element and named it iode, from the Greek word "ioeides or iodes" for violet color (MacMillan, 1970). The world production is not known with any great certainty, but it is probably between 25 and 35 million lb per year, of which about 30% is consumed in the United States. Geology and Mineralogy Iodine compounds occur as a minor constituent as a mineral in the Chilean nitrate deposits and in solution in brines and seawater. According to the US Geological Survey, it is the 47th most abundant element in the earth's crust. The minerals lautarite, Ca (I03)3 (calcium iodate), and dietzeite, Cat (103)2 (CrO4), (calcium iodate-chromate) are found in Chilean nitrate deposits which are located in Antofagasta and Tarapaca provinces on the eastern slope of the coast range in a desert area. Various brines contain iodine compounds. Seawater contains about 0.05 ppm of iodine and some seaweeds will extract and accumulate it up to 0.45% on a dry basis. Some coals in West Germany also contain iodine compounds. The known and potential sources of iodine reported in 1968 are given in Table 1. Table 2 lists estimated world iodine reserves. Iodine has been recovered from brines in Java, Indonesia, France, England, and the USSR. Iodine has also been recovered from seaweed in Ireland, Scotland, France, Japan, Norway, and the USSR. The indicated reserves and future resources of iodine are large but have never been adequately measured. Analysis Iodine as the free element can be detected by the characteristic blue color it gives to a starch solution. Quantitatively it is determined as the free element by titration with standard thiosulfate solutions using starch as an indicator. Colorimetric methods are also applicable. Markets and Prices Iodine and its compounds are generally marketed in the form of: iodine, crude; iodine, resublimed; calcium iodates; calcium iodide; potassium iodide, sodium iodide, and numerous organic compounds. Product Specifications Crude iodine, World market: 99-99.5% 12. Crude iodine, US produced, average: 99.8% 12. Crude iodine, USP XVII Specs: not less than 99.8% percent I2. Resublimed iodine is usually 99.9% and ACS specifications call for not over 0.005% total bromine and 0.020% nonvolatile materials (Anon., 1971). Prices, c.i.f. United States, for iodine have been steadily increasing from $1.18 per lb of crude in 1967 to $6.37-7.27 in January 1981 (Anon., 1981). In 1980 the price of iodine increased by 50%.

Jan 1, 1983

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg's second method, though superior to his first, necessitates a large number

Jan 1, 1946

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg's second method, though superior to his first, necessitates a large number

Jan 1, 1946

By E. A. Almond

An attempt is made to explain the effect of stress on strain aging by examining the mechanism of yielding for a group of aged dislocations. The experimental results on which the theory is based indicate that a linear relationship develops between the aging stress and the discontinuous yield effect in a low carbon steel THE discontinuous yield effect that occurs in bcc metals after strain aging is usually explained by the interaction of interstitial atoms with individual dislocations. Attempts have been made to interpret the kinetics of strain aging in terms of interstitial segregation to nonrandom groups of dislocations1-3 but apart from Li's4 work little or no effort has been made to examine the effect of groups of aged dislocations on mechanical properties. It appears likely that such groups can be stabilized if a positive load is maintained on the specimen during aging5 and, furthermore, that the enhanced strain aging effect associated with aging under load might be due to the stability of these aged groups. The effects associated with this latter phenomenon have been described by Almond and Hull, Ref. 5, Figs. 2 and 3, and it is found that the upper yield stress, the lower yield stress, and the yield point elongation are increased by aging under load. The yield point elongation reaches a maximum value but the enhanced effect persists in the upper and lower yield stress values even after extended aging treatments when the general level of the flow stress curve rises. The flow stress, as measured at 8.5 pct total strain, however, is independent of aging stress. Almond and Hull5 showed that it was unlikely that the differences in mechanical properties could be caused by stress enhanced diffusion and they suggested that the effect was in some way associated with the different dislocation distributions that are obtained when specimens are aged with and without an applied stress. At that time no explanation was offered for the strengthening effect produced by stabilized dislocation distributions but additional tests have been performed to establish a quantitative relationship between aging stress and mechanical properties, and also to examine more closely the effect of varying the procedure for applying the aging stress. EXPERIMENTAL The material used was an iron wire containing 0.015 wt pct C, 0.002 wt pct N, and 0.006 wt pct 0. Tensile specimens with a 1 cm gage length and 0.08 cm diam were annealed at 850°C for 1 hr in vacuum to establish a grain diameter of 0.032 mm and then aged at 200°C for 24 hr. After this treatment the amount of carbon left in solution would be less than 10-4 wt pct, and ni- as aging time is increased. It is suggested that this observation, and effects that arise from varying the method of applying the aging stress, can be explained by a strengthening mechanism whereby dislocations are more difficult to move when they are aged in piled-up groups. trogen would be the main cause of strain aging. Tensile tests were performed in a hard beam machine at a constant crosshead speed of 0.02 cm per min and the specimen chamber was immersed in a temperature controlled silicone oil bath at 32" * 0.05"C. RESULTS All specimens were prestrained 5 pct before aging under stress and the results in Figs. 1 to 5 show the effect of aging time and aging stress on the following parameters ?UY = auy — ?F(5); i.e., the difference between the upper yield stress after aging,?uy, and the flow stress after prestraining 5 pct, ?f(5). ?LY = sly —sf(5); the difference between the lower yield stress after aging, ojy, and the flow stress after prestraining 5 pct. s8.5 = the flow stress at 8.5 pct total strain after aging at 5 pct strain. Varying the Loading Procedure. Three variations in the procedure for applying the aging stress were examined; i) After prestraining, the specimen was unloaded to a stress of 18 kg mm-2, aged at that stress, and then tested. ii) After prestraining, the specimen was unloaded to 2 kg mm-" then reloaded to 18 kg mm-', aged at that stress, and tested. iii) After prestraining, the specimen was unloaded to 18 kg mm-', aged at that stress, then unloaded to 2 kg mm- before testing. Specimens were unloaded or reloaded by decoupling a clutch in the drive transmission of the tensile machine. This enabled the crosshead to be driven manu-

Jan 1, 1970

By Alexandre Pourcel

The perusal of Mr. Willard P. Ward's " Notes on the Behavior of Manganese to Carbon," presented at the Washington meeting of the Institute in February, 1882, has suggested further reflections on the same general topic, and has led to the preparation of the present paper. The same observation that Mr. Ward has put on record in his "Notes" was also made by myself at about the same time (in August, 1875), and under almost the same conditions. From a blast-furnace that was very hot, as was the furnace mentioned by Mr. Ward, I obtained a pig-iron containing about fifteen per cent. of manganese, gray in color, and very tough. It could be pulverized, but could not be cut with the chisel. I analyzed this iron and found that it contained, as I had suspected,a large amount of silicon. From this fact I drew the conclusion that the silicon had deprived the manganese of its power of dissolving carbon, since the latter, instead of occurring in the pig in combillation, appeared as graphitic carbon. I thus saw reproduced on a large scale, and demonstrated in a visible way, the property that Colonel Caron, a French scientist, had discovered in silicon,—the property of obstructing the process of hardening in steels by keeping the carbon in the graphitic condition. An attentive study of the conditions under which the phenomenon observed by Mr. Ward takes place led me to go back to operations of synthesis, and to make as I wanted them pig-irons containing varying quantities of silicon, manganese, and carbon. An iron, thus prepared, was intended to serve me as a chemical reagent in the production of steels cast without blow-holes, such as my lamented friend, Mr. A. L. Holley, has introduced and made known to the United States. What I needed in order to make very soft steels, cast without blow-holes, was an iron which, when it was added to the bath of steel, introduced into the bath a sufficient amount of silicon and of

Jan 1, 1883

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansen1 and Haughton,2 the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 257.3°C ± 0.1°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys,4,5 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157.2°C ± 0.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4'C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. THERMAL ANALYSIS Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high flash point was used. A platinum-platinum rhodium thermocouple 0f fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermo-couple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.2°C, and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it seems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16r, in. thick, sufficed to give a cooling rate of from 1° to 2°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By J. A. Cahill, A. D. Kirshenbaum

Using an alumina or zirconia crucible with an alumina sinker or a molybdenum sinker coated with zirconium dioxide, the density of liquid iron was determined by the immersed-sinker method over the temperature range of 1800" to 2500°K. The density, with respect to temperature, is ex-Dressed by the equation Dg/cm = 8.523 - 8.358 X 10 T'K The molar Volumes and thermal coefficients of expansion were calculated. Iron, upon me1ting, was found to expand 3.5 pct. A basic knowledge of the physical properties of materials at high temperatures is becoming increasingly important. A check of the literature shows, that in spite of the importance of iron, very few measurements have been made of its physical properties in the liquid state. Density measurements have been made by Benedicks and his collaborators1g using the method of balanced columns, by Desch and smith4 using the immersed sinker method with an alumina sinker, by Lucas using the maximum bubble method5 and by Stott and endall' who used an alumina pyknometer. In the method of balanced columns, the difference in level of molten iron in two arms of a U-tube, together with the corresponding difference of pressure had to be measured. The formation of gas bubbles in one or both arms was a great source of error. These values are very erratic. They vary from 6.83 to 7.45 g per cm3 at the melting point (1805"~) and from 6.45 to 7.15 g per cm3 at 1890°K. Stott and Rendall determined the density at 1837"K, with a reproducibility of *0.2 pct. They used an alumina pyknometer fired to 1973°K. The vessel was filled in a vacuum furnace by immersion in the liquid metal. When thermal equilibrium was attained, the pyknometer was withdrawn, cooled, the ingot removed and then weighed. The chief disadvantage of the method was the difficulty of inserting the pyknometer without cracking it. The authors have been able to determine the density of liquid iron from its melting point up to 2500°K, by using the immersed-sinker method, with A1203 or ZrOz crucibles and A1203 or molybdenum sinkers coated with Zr02, Fig. 1. EXPERIMENTAL Apparatus. In these studies the source of heat was the carbon tube resistance furnace with an argon atmosphere described previously.7 Experimental runs were made using either Ala3 or ZrOz crucibles. The sinkers used were 1) pure A1a3 and 2) molybdenum coated with ZrOz. The crucible, 2 1/8 in. in diam and 3 in. high, was centered in the furnace on an Ala3 of Zr02 pedestal. The sinker, 1/2 in. in diam and 1 1/2 in. long, together with a counter weight, was suspended from an analytical balance into the melt by a molybdenum wire. Procedure. The procedure, as described previously,' consisted in measuring the weight loss of the sinker in the liquid iron while determining simultaneously the liquid iron temperature by means

Jan 1, 1962

By Horace R. Graham

CHEMICAL nitrogen and the "nitrates" of commercial significance are derived mainly from three basic sources: (1) the natural deposits in the form of nitrate-bearing earth and clay, which, being largely water-soluble, can exist only in the most arid portions of the earth; (2) coal, which yields not only nitrogen but also the additional by-product hydrogen required for the synthesis of ammonia and its compounds; (3) the atmospheric air, which contains 75.5 pct by weight of pure nitrogen gas. NATURAL NITRATE DEPOSITS Occurrence Although natural nitrate deposits consisting principally of the salts of sodium and potassium have been reported in Egypt, South Africa, Mexico, Argentina, Colombia, Peru and the USA, the only known natural nitrate resources of commercial importance are the vast deposits found in the Atacama, Tarapaca and Antofagasta regions of northern Chile, lying in a narrow strip 10 to 50 miles wide and roughly 450 miles long, between latitudes [19O] and [26OS]. In addition to yielding nitrates of sodium and potassium, these deposits are the source of the major portion of the world's supply of iodine. The nitrate-bearing ores known in Chile as caliche are variable in composition and may contain from 5 to 30 pct each of nitrate, chloride and sulphate. While the deposits are present chiefly in the form of the sodium salt, potassium, magnesium and calcium also occur in percent- ages from 0.1 to 5; usually as double salts with sulphate, which are but slightly soluble in nitrate leach solutions. These double salts are bloedite(Na2S04.MgS04.4H,0), glauberite (Na2S04.CaS04), polyhalite (K2SO4.- MgS04.2CaS04.2H20). Some deposits contain up to30 pct of their ni-

Jan 1, 1949

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations'j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.' Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.' Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini's work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969

BECAUSE you cannot always proceed by the ordinary pathway since you sometimes find yourself in a place where you cannot have all that you might need or wish, it often happens that it is necessary to know how to recognize and understand your materials well, in addition to having them well disposed, and to know how to use your, ingenuity in arranging a mould., Furthermore, things have a great diversity among themselves, and it is not possible to give a particular rule for all. But if you have a certain broad fundamental knowledge when you have need of many things, the ingenuity awakens and supplies its needs by imitation. Now, because I have thought that you had not hitherto had the slightest shadow of knowledge of what I have described in this treatise of mine, I have expanded and narrated things in greater detail than perhaps I might have done. For this reason I have also decided that I wish to tell you of several methods that can be used if you wish to mould, especially in making an intaglio* for a relief, t or in making another intaglio in bronze from either an intaglio or a relief. And I will tell how every relief reduces, itself from convex to concave and also how the relief is made from the intaglio. These works are first made of plaster or pastes or some other liquid thing that is soft when moulded and becomes hard either by drying out with heat or by shrinking with cold, such as tragacanth, plaster of Paris, sulphur, lead, wax, or similar things. And, in conclusion, we describe the method of making an intaglio from a solid. In making an intaglio you must first consider whether it is a large or small thing, figure or foliage, whether it is in demi- or bas-relief, and whether it is a thing that projects from the mould wholly or in part.

Jan 1, 1942

By AIME AIME

FOLLOWING careful study of the relations of the Institute to students and the younger members of the profession, the Membership Committee recommended to the Board a change of plans abolishing the Junior Associate class of membership, substituting a -Junior membership and providing for Student Associates. The Board adopted this report at its meeting on Nov. 23, and asked Counsel to draft the necessary amendments to the By-laws, and gave formal notice of intentions to amend as provided in Section I, Article XI1 of the existing By-laws. The By-laws as it is proposed to amend Article I, 11, 111, IV, X, and XI follow. The new plan requires no changes in the other Articles. The matter will come before the Board for vote on Jan. 25.

Jan 1, 1929

By N. A. D. Parlee

THE gas-liquid metal diffusion cell technique1-3 has been used to study the diffusion of nitrogen in Fe-C alloys. The actual apparatus and technique were the same as employed by the authors to study the diffusion of hydrogen in liquid iron.' The diffusion cell' was formed by immersing an alumina tube in a stagnant melt contained in an alumina crucible. The tube (hereafter called absorption tube) contained nitrogen gas at 1 atm and was connected to a sensitive gas-measuring system. The change in the average concentration of nitrogen in the melt in the absorption tube was determined by measuring the rate of absorption of nitrogen in the diffusion cell. Eq. [I], 1-3 derived from the appropriate solution of Fick's second law, was used to examine the data and to calculate chemical diffusion coefficients (D) in situations where the absorption appeared to be controlled by diffusion in the liquid: where V is the stp volume in cu cm, d is the diffusion cell diameter in cm, p, is the density of the melt in g per cu cm, pg is the stp density of nitrogen in g per cu cm, C, is expressed in wt pct, D is in sq cm per sec, and t is in min. According to Eq. [I], a plot of v vs vt should yield a straight line passing through the origin if absorption is controlled by diffusion in the liquid. The slope of this line could be used to determine the value of D under appropriate conditions. As discussed in earlier reports,1,2 the initial thermal expansion of the gas upon immersing the absorption tube distorts the line in the initial stages of a diffusion experiment. However, this is not a serious problem since the slope of V vs 6 plots can be determined from the data points obtained after the initial expansion ceases. The volumes reported on the data plot presented here represent absorption after this thermal expansion ceased. Several preliminary diffusion experiments were attempted with melts of pure iron and with Fe-C alloys containing up to 0.6 pct C. In these cases, no or very little absorption was observed. The only data obtained were for an Fe-C melt which was in addition thoroughly deoxidized by successive hydrogen and vacuum-degassing treatments. These treatments introduced an appreciable amount of aluminum into the melt and reduced its omgen content. The original charge material for this melt contained 0.23 pct s and approximately 0.001 pct &. After repeated hydrogen and vacuum-degassing treatments two diffusion experiments were performed. The analysis of the melt

Jan 1, 1968

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970

Jerome L. Boyer, Reading, Chairman; William L. Sheafer, Pottsville, Secretary ; Levi Quier, Reading, Treasurer; Robert Allison, Port Carbon; James Archbald, Jr., Pottsville; William Atkins, Pottsville; D. P. Brown, Lost Creek; William McH. Boyer, Rending; Albert Broden, Reading; George Brooke, Birdsboro; Frank Carter, Pottsville; H. P. Cooper, Pottsville ; J. H. Carpenter, Reading; E. S. Cook, Pottstown; B. Halberstadt, Pottsville; Hakon Hammer, Pottstown; J. Hartshorne, Stowe; M. P. Janney, Pottstown; R. C. Luther, Pottsville; N. Muhlenberg, Reading ; W. H. Morris. Pottstown ; George L. Norris, Reading; G. H. Potts, Pottstown ; H. Potts, Pottstown; S. M. Riley, Ashland ; J. S. Robeson, Pottstown ; Jas. P. Roe, Pottstown; A. W. Sheafer, Pottsville; Heber S. Thompson, Pottsville; Bard Wells, Pottsville; E. C.Wagner, Girardville; N. B. Wittman, Birdsboro. Reception Committee.— George Brooke, Chairman; Robert Allison, J. H. Carpenter, Edgar S. Cook, R. C. Luther, W. H. Morris, H. S. Thompson. Hotel Headquarters.—The Neversink Mountain Hotel, near Reading, Pa. All sessions were held in the hotel. The opening session was held on Tuesday evening, October 11. Mr. Jerome L. Boyer, Chairman of the Local Committee, called the meeting to order, and introduced Mr. John F. Daniel], Jr., VicePresident of the Reading Board of Trade, who delivered an address of welcome, in the course of which the industrial and commercial importance of the city was effectively outlined by skilful use of the statistics of leading branches. From this statement the following particulars are condensed for preservation: The Board of Trade has about 300 members. The annual value of the manofttctures (taking mainly the figures of 1891) is as follows: Iron manufactures, about $16,000,000 (including boilers and flues, $323,000; hardware, locks and butts, $1,650,000; pig-iron, wrought-iron pipe and machinery, $8,400,000; beams, bridge-work and steel, $4,000,000; bolts, nuts, rivets, etc., $1,000,000; stoves, $659,000); silk and cotton goods, $1,725,000; boots and shoes (one concern only), $150,000; ropes and cordage, $600,000; fire-brick, terra-cotta and glass, $320,000; wool and fur hats, $3,000,000; cigars (105 millions), upwards of $3,150,000. The street and elec-

Jan 1, 1893

By M. E. Wadsworth, D. R. Wadia

The rate of reaction of cuprite was measured in a series of sulphuric acid solutions, from which oxygen had been excluded, at various concentrations and temperatures. The overall reaction CuzO + H2S04 + Cu " + CuO + H20 + So4' may be explained quantitatively by two simultaneous rate reactions involving not only H+ but also the hydrolytic adsorption of H2SO4. The results indicate the importance of considering surface mass balance relationships associated with heterogeneous surface reactions. T EACHING has long been an important method for the recovery of metals from certain minerals. Many processes have assumed minor importance in modern practice but such operations as the recovery of uranium and present interest in high pressure-high temperature solution of sulphides' ' well illustrate the importance of leaching as a unit operation. Little quantitative information is available in a form sufficient to determine the mechanism of solution at the solid-aqueous solution interface for given systems. For this reason, it is important that fundamental studies of leaching processes be conducted so that parameters associated with such surface reactions may be understood and correlated. Cuprite was chosen for this study as a result of a recent investigation carried out at the University of Utah on ores of the Ray and Chino Mines Divs. of the Kennecott Copper Corp. These sulphide deposits contain sufficient oxidized minerals, such as cuprite, malachite, and azurite, so that recovery of metal values contained in the oxidized fraction is of primary interest. Of these oxides, cuprite (Cu,O) is the most interesting, since it dissolves in sulphuric acid by an oxidation reduction couple resulting in the formation of 50 pct metallic Cu and 50 pct cup-

Jan 1, 1956

By J. Rogers. K. L. Sutherland, E. E. Wark, I. W. Wark

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts 'he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By E. E. Wark, I. W. Wark, J. Rogers. K. L. Sutherland

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts 'he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By G. R. M. Del Giudice

The term "slime-coating" is not new in the art of flotation; the phenomenon has been observed and described by Taggart;(l)† Taggart, Taylor, and Ince;(2) and by Ince.(3) Notwithstanding that flotation was introduced for the treatment of finely crushed ore, the adverse effects of slimes have been recognized since the earliest days of the process, and the Elmore, Delprat, Potter, and other processes actually specified desliming of the ore prior to treatment. The cause of this trouble has been studied and described by Taggart;(1) Taggart, Taylor, and Ince;(2) Ince;(3) Morrow and Griswold;(4) and by Gaudin and Malozemoff.(5) Old Theory of Slime-coatings At present, so far as published work shows, there seems to be but one theory for the mechanism of slime-coatings. Ince(3) states that they are due to attraction between electrostatic charges of opposite sign on the sulfide and on the slime particles, supporting this theory by migration experiments in the Burton tube. He also used the microscope in conjunction with a glass cell employed by Beans and Eastlack(6) in studying migration, but met with interference from endosmosis. Several attempts have been made in the Department of Mineral Dressing at Columbia University to duplicate Ince's experiments with the Burton tube, but the results have never been convincing. Formation of precipitates which settled through the pulp levels, and evolution of gas at the electrodes, which disturbed the interface between the pulp and the distilled water above it, seriously interfered with observations. However, by use of the migration cell shown in Fig. 1, endosmosis effects and the disturbances due to precipitation and gas evolution were avoided, and distinct and reproducible migrations or absence of migration were observed. The cell was made of bakelite and had platinum electrodes. Objectives were employed which had a working distance of at least three millimeters,1 and the parts of the mounting which came in contact with

Jan 1, 1935