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By J. Rogers, H. F. A. Hergt, K. L. Sutherland

In 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group — SO4- or — SO3- are excellent collectors for cassiterite and promise to be selective. The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000-gram Denver cell. Experimental Methods Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously de- scribed.5,10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these the determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver SUbmachines,—Melboume tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By A. C. Fieldner, Lester L. Hirst, Henry H. Storch

Experimental work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogehation of bituminous coal and tar by the Bergius-I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 Ib. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydro-genation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. Equipment and General Procedure of Research The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By Lester L. Hirst, Henry H. Storch, A. C. Fieldner

Experimental work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogehation of bituminous coal and tar by the Bergius-I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 Ib. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydro-genation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. Equipment and General Procedure of Research The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By B. Post, F. W. Glaser

Three borides of zirconium have been reported: ZrB,l ZrB2,2,3 and ZrB12, 4 The phase relationships, ranges of stability, and some physical properties of these compounds are described. THE zirconium borides differ considerably from one another, particularly with respect to their relative stabilities at high temperatures in the presence of carbon.4,5 ZrB2 is extremelv stable at all temperatures (to the melting point) in contact with carbon. Both ZrB and ZrB12 tend to decompose at elevated temperatures when carbon is present in excess of about 0.5 pct. ZrB forms ZrB2 and ZrC, and ZrB12 decomposes to form ZrB2 and a boron-carbide phase. In the ZrB12 preparation, boron present in excess of that needed to form ZrB2 reacts with carbon, if present, to form carbides, in preference to forming the higher boride. Similar instability of borides, other than diborides of the transition metals of the 4th and 5th groups of the periodic table, has been reported.5,6 special precautions had, therefore, to be taken to minimize carbon contamination in the preparation of ZrB and ZrB12. Reactions below 1400°C were carried out by heating powdered mixtures of zirconium hydride and boron in quartz tubes in a hydrogen atmosphere. For temperatures above 1400°C, reactions were carried out in graphite molds. Carbon contamination from the molds was minimized by employing extremely rapid heating rates to reduce carbon diffusion into the body of the specimen, and by subsequent "shaving" of sample surfaces that had been in contact with the graphite dies. A heating rate of about 2000°C per min was obtained by heating the dies (by direct conduction), using a current of 40,000 amp. Although this type of heating cycle apparently allowed little time for "homogenization," close approximations to equilibrium conditions were usually obtained as a result of the very strongly exothermic reactions between zirconium hydride and boron at elevated temperatures. Reproducibility of results in repeated runs under varying conditions was taken as a reasonable indication that equilibrium conditions had been effectively achieved. Quenching was accomplished by rapidly immersing the entire die, containing the reaction products, in water. Specimens could also be cooled at controlled rates by adjustment of the rate of flow of water through the water-cooled copper electrodes in contact with the graphite dies.

Jan 1, 1954

By John L. Lamont, Walter Crafts

SELECTION of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of hardenability,1 as-quenched hardness,2,3 and tempered tensile strength.4 Ductility and toughness may also be estimated if the steel is completely hardened on quenching,5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In fine-grained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accompanied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to 4 in. in diameter. PROCEDURE The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1o30, 1040, 1340, 3310, 3316, 4320, 4330, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 9310, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.35. The bars were tempered as follows: ½ in., I in., and I 5/8 in., 2 hr; 2 ½ in., 3 hr; 4 in., 5 hr. All bars were air-cooled from the tempering tem-

Jan 1, 1947

By J. H. Frye, R. M. Treco

ONE of the chief hindrances to an understanding of the hardness of solid solutions is the sparsity of suitable hardness data. There is great need of a large body of hardness data obtained from many different alloys of high purity by identical testing methods and corrected to correspond to a single grain size. A considerable amount of such data has been obtained by means of the Meyer analysis on copper-rich and silver-rich solid solutions. There are enough of these data to permit comparison of numerous alloys at equal solute concentration in these two solvents, but only in a few cases is it possible to construct hardness-concentration curves for any given alloy. Therefore additional hardness work on most of these alloys is desirable. The primary solid solutions of silver with cadmium, indium, tin, or antimony as solute are of special interest, since all elements are from the same period of the periodic table and since, as shown previously,1 the hardening effect of equal percentages of these solutes is proportional to the lattice expansion produced by them. This paper presents the relation between hardness and concentration in the silver-antimony system from very dilute to nearly saturated solutions of antimony in silver. EXPERIMENTAL PROCEDURE Alloys were made from silver, 99.99 per cent pure, and antimony, 99.975 per cent pure. Silver and antimony were placed in graphite crucibles that had an ash content of less than 0.75 per cent. These metals were melted and allowed to solidify in a vacuum, which, after melting was complete, was usually equivalent to 3 mm. Of mercury. A high-frequency furnace was used. The ingots so obtained were worked and annealed to lessen segregation and to control grain size. Annealing was done in evacuated and sealed glass tubes. Hardness measurements on specimens from these ingots were by means of the Meyer analysis.3,4 Using a 4-mm.. ball, impressions were made under seven loads from 25 to 400 kg. The diameter of impression made under each load was measured. This enabled calculation of the constants in the well-known formula of Meyer. L=ad¬n where L = load, d = diameter of impression, a = a constant, n = a constant The Meyer hardness is defined as P = L/(1/4pd2) or P = 4adn-2/p Meyer hardnesses corresponding to d = 1 and to d = 4 are of especial interest, since the first corresponds to comparatively slight plastic deformation and the second to the maximum plastic deformation producible by penetration of the ball. These

Jan 1, 1944

By R. I. Jaffee, R. W. Wood, H. R. Ogden, D. N. Williams

D. W. Morgan, D. H. Polonis,and R Taggart (Uuivevsity of Washington)—Dispersion hardening in titanium-copper alloys is of particular interest to us in view of our current research activities in phase transformations in this system. We should like to raise questions concerning several points in the paper. The flow sheet for fabrication and heat treatment (Authors' Fig. 2) indicates that 0.045 in sheet is treated in air for a period of 30 min at 1625' F. Were any surface coatings used to reduce oxygen contamination at this stage? One might ask the same question about the 8-hr annealing at 1400F. Contamination during fabrication and heat treatment of such thin sections could be considerable without some protection. Although the authors state that no analyses were made, they note that contamination masks the distinction between base strengths of the different alloys. In this connection, what fabrication and heat-treatment procedures were used in obtaining the comparison specimens of unalloyed titanium? It would seem that oxygen contamination must cast doubt on the reliability of the proposed strength-mean free path relationship deduced from the data (Authors' Fig. 5). It is usual to evaluate dispersion hardening on the basis of yield strength rather than ultimate tensile strength, and accordingly we have replotted the authors' Fig. 1 to include yield strength. The yield strength data do not justify a discontinuity of 3 p at either 70" or 1000 OF. Can the authors substantiate their conclusion 1) with additional evidence? Otherwise it seems that they have succeeded only in pointing out the possibility of a linear relationship between yield strength (or Uts) and the logarithm of the nleall free path, comparable with that demonstrated for iron-carbon alloys (Authors' Ref. 2). Work in our own laboratories has shown that the hardness of the phase Ti,Cu is 235 Vpn, and that of a 1.5 pct (at.) (2 pct wt) supersaturated solid solution of copper in titanium is 190 Vpn. This small difference in hardness would suggest that Ti2Cu should not be a very effective dispersion-hardening phase. D. N. Williams, R. W. Wood, H. R Ogden, RI. L Jaffee (authors' reply)— This discussion brings out some interesting points with respect to the interpretation of our results, and also raises some questions regarding the experimental technique. We shall consider the latter questions first. Contamination during heat treatment was prevented by performing all heat treatments in argon-filled Vycor capsules. Fabrication was done in air, with the usually observed scaling. Scale was removed

Jan 1, 1962

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. Rogers, H. F. A. Hergt, K. L. Sutherland

IN 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group -SO4- or _S03- are excellent collectors for cassiterite and promise to be selective.1 The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000gram Denver cell. EXPERIMENTAL METHODS Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously described.5-10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these tests determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver Submachines.--Melbourne tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By O. Vartianen, R. T. Hukki

A preliminary investigation of the collecting effects of various fatty acids in tall oil has led to a conclusion that the collecting power of fatty acids used in flotation increases with increasing un- saturation of the hydrocarbon chain. Linoleic acid was found to be an excellent collector for oxide minerals. TALL oil is a mixture of fatty and resin acids extracted as byproducts in the sulphate pulp industry. In the field of flotation a well-known example of this type of product is Reagent No. 708 of the American Cyanamid Co. Its successful use as a flotation collector with many nonsulphide minerals has been described by Falconer and Crawford.&apos; The composition of crude tall oil varies within wide limits.&apos; " By a number of methods the crude oil may be refined to produce a variety of refined products. This investigation presents a preliminary comparative study of collecting properties of the fatty acids in tall oil. In Finnish tall oils these constituents are primarily palmitic, oleic, linoleic, and linolenic acids.:&apos; The first is a saturated fatty acid having 15 carbon atoms in its hydrocarbon chain, plus one in the carboxyl group. The others have 17-carbon-atom chains and are unsaturated. It is of particular interest to note that palmitic, oleic, lino-leic, and linolenic acids represent increasing degrees of unsaturation with 0, 1, 2, and 3 double bonds, respectively. To test the collecting properties of the four fatty acids separately, the vacuum flotation technique described by Schuhmann and Prakash4 was used. By this method the boundary between flotation and non-flotation conditions was approximately delineated, with the use of ilmenite and several other minerals. Collector concentration and pH were the principal variables. On the basis of information obtained, actual flotation tests were run on an ilmenite-bear-ing ore in a laboratory flotation cell. Through the courtesy of P. Kajanne from the Department of Chemistry, Finland Institute of Technology, the following reagents were obtained for this investigation: 1—Palmitic acid, of Judex, had a purity of 95 pct as determined by parallel iodo-metric and spectrophotometric measurements. 2— Oleic acid, product of May and Baker Ltd., indicated purity of 98 pct. By iodometric and spectrophoto-metric determinations the oleic acid content was found to be 83.8 pct. In addition, it contained 6 pct linoleic, 1 pct linolenic, and 9.2 pct saturated fatty acids.&apos; 3—Linoleic acid was prepared from soybean oil by low-temperature crystallization. Its linoleic acid content was 95 pct by the methods indicated above. 4—Linolenic acid was prepared from linseed oil by low temperature crystalIization. Its linolenic

Jan 1, 1954

By William Kent

(Read at the Amenia Meeting, October, 1877.) IN a paper by Mr. Frank Firmstone, published in vol. iv, of the Transactions of the Institute, on "Comparison of Results from Open-topped and Closed-topped Furnaces," the regularity of the average grade of pig iron produced by the furnace under different conditions is expressed by means of a curve or diagram. The object of this note is to show that the graphic method, or that of representing variations by plotted curves or diagrams, is capable of a much more extended application to blast-furnace records, making a valuable auxiliary to the "furnace .book," and that by it the practical metallurgist may obtain at a glance information concerning the variations of the furnace during long periods, which could be found in the furnace book only after a tedious search. Plate XII is a graphic record of an anthracite blast furnace for one month. The table on page 554 gives the figures obtained from the furnace book, together with a record of temperature of the atmosphere, barometric pressure, and moisture in the air, which was obtained from a meteorological observatory not far from the furnace. In the records of a furnace, two of the variable qualities are final results, viz., the quantity of pig iron produced, and its grade; all the other variables are antecedent causes which produce the final results. Of these variable causes which contribute to the quantity of product and its grade, some are partially under the control of the furnace manager, others depend upon the state of the atmosphere, and still others are accidental. Of the first class are the character of the materials charged, and their relative proportions, their mechanical conditions, as wet or dry, large or small pieces, etc., the revolutions of the engine, the heat and pressure of blast, and the distribution of the charge. Of the second class are the number of pounds of air blown into the furnace for each stroke of the engine, the amount of moisture in the air, and the condition of the chimney draughts. These vary largely with the season of the year. Of the third. class is the leaking of a tuyere or a temporary stoppage. To keep a record of this kind for a whole year, it is only necessary to procure a sheet of common profile or cross section paper, about 38 inches long and 8 or 10 inches wide, with cross lines ruled about 0.1 of an inch apart. The vertical lines, or those in direction of the

Jan 1, 1878

By S. Leber, R. F. Hehemann

Diffusion coefficients for the Cb-W system were measured using couples prepared from poly crystalline, commercially pure metals. The diffusion coefficients, measured in the temperature range between 1700° and 2300°C, decreased exponentially as the tungsten concentration was increased from 0 to 50 at. pct, then decreased abruptly at higher concentrations. A decrease of two orders of magnitude was observed over the entin? compositional range. The diffusion coefficients were in the range defined by the self-difiusion coefficients of the individual elements, indicating their general validity. An activation energy of 60,500 cal per mole was measured for the 20 pct W composition. Such low values, when compared with energies over 100,000 cal per mole for the pure constituent elements, indicated that transport mechanisnzs more rapid than volume diffusion were contributing substantially to inter dijfusion. Difference should, therefore, be expected between these data and the intrinsic diffusion coefficients. These differences should be significant in the kinetics of &apos;transport phenomena in practical systems. CONSIDERABLE attention has been devoted in recent years to the mechanical behavior and other properties of the refractory metals and their alloys. The Cb-W system has been of special interest as a base for the development of more complex compositions of commercial interest. In spite of the importance of mass transport to all aspects of elevated-temperature behavior, and especially to the production of alloys by powder-metallurgy techniques, little attention has been paid to diffusion in the Cb-W system. Results from a previous study of this system1 appeared to be anomalously high. The present investigation is, therefore, an attempt to obtain more accurate diffusion coefficients in this system. Intrinsic diffusion coefficients, of primary importance from the theoretical viewpoint, can only be obtained accurately from studies utilizing compositional gradients approaching zero. However, many practical problems involve diffusion under significant concentration gradients. The diffusion coefficients determined in this investigation were, therefore, obtained from couples prepared from elemental metals. The data obtained should be of value in the analysis of problems such as homogenization during powder-metallurgy alloying or reactions between base and clad in coated structures. In this vein, the investigation was conducted on poly crystalline materials of commercial purity. PROCEDURE Diffusion couples were prepared by sandwiching a columbium sheet between two sheets of tungsten. The composite was welded around all edges, the tungsten forming a protective can for the columbium. The composite was soaked for 4 min at 1600°C in a hydrogen-atmosphere furnace, quickly forged to 40 pct reduction in thickness, and then rapidly cooled to room tempera-

Jan 1, 1967

By W. D. Robertson

THE effect of a tensile stress in accelerating the corrosion-cracking of certain alloys of aluminum, magnesium and iron is widely recognized. The literature is extensive and it is only necessary to cite the recent ASTM-AIME Symposium.1 There are, however, no experimental data conclusively showing the effect of an applied compressive stress. It has been inferred, from the generally accepted mechanism postulated for the acceleration of corrosion by an applied tensile stress, that a compressive stress would inhibit corrosion. Furthermore, it is observed that corrosion cracks invariably start on the tension side of a specimen bent as a simple beam. This observation has led to the suggestion that shot-peening of the surface would inhibit or eliminate stress-corrosion cracking in magnesium alloys, and aluminum alloys.3 However, the degree of inhibition produced by shot-peening does not appear in the literature except for the above qualitative references which are unsupported by experimental data. Moreover, while peening undoubtedly imposes a surface compressive stress, the alteration of the surface by the severe cold-working involved complicates the interpretation of the results with respect to the effect of a compressive stress alone. If corrosion proceeds along preferential paths produced by precipitation from solid solution, it is easily understood how a component of tensile stress normal to these paths will accelerate the corrosion and lead to ultimate failure. On the other hand, if the metallurgical conditions are such as to create preferential corrosion paths, then it is difficult to understand how a compressive stress, produced by shot-peening or any other method, can inhibit corrosion except in the sense that the accelerating factor is removed. Thus, if the basic corrosion mechanism remains unaltered, there should be little or no inhibition resulting from the application of a compressive stress if in¬hibition is defined as the reduction of the degree of corrosion below that experienced in the unstressed state. The experiment described below was performed to isolate and evaluate the effect of a compressive stress on the corrosion and stress-corrosion cracking of a high strength aluminum alloy (24-S); and, by a comparison of the corrosion rate of specimens subjected to an applied tensile stress, compressive stress and in the unstressed state, to clarify the role of stress in intergranular corrosion. EXPERIMENTAL PROCEDURE The experiment was conducted with the aluminum-copper-magnesium alloy known as Duralumin 24-S.* Specimens, 0.064 in. thick, in the form of I in. wide strips sheared parallel to the rolling direction,

Jan 1, 1947

By G. K. Engelhart

A multi-stage counterflow process developed in Germany preheats dry pulverized portland cement raw materials held in suspension in rotary kiln waste gases. Capacity of the first kiln installed for this purpose in the United States has been increased from 860 to 1500 bbl per day, with fuel reductions from 1,100,000 Btu to 650,000 or 700,000 Btu per bbl. Sixty percent of total waste gas is used. As full use of the gas stream is approached, additional kiln production and fuel economy may be expected. EFFECTIVE use of rotary kiln waste gases to preheat dry pulverized materials has been demonstrated in full-scale operation at the Allentown Portland Cement Co. plant, Evansville, Pa. Pulverized raw materials are preheated in suspension in the gas stream in a multi-stage counterflow process which draws the gases through a series of cyclone collectors. Upon entering the first cyclone stage the material, continuously delivered and suspended in the gas stream, is successively collected and re-suspended until it discharges through the kiln feed pipe. Gas and material contact time is thus prolonged, providing a high degree of heat recuperation with a very low temperature differential between gas and material at the final stage. The suspension preheater, developed by Klock-ner-Humboldt-Deutz AG of Cologne, Germany, was first installed at the Norddeutsche Huette plant, Oslebshausen, Germany. Similar preheaters are now in operation at three other German cement plants. The first American installation, at the Allentown Portland Cement Co. plant, was designed and manufactured by Fuller Co. of Catasauqua, Pa., Humboldt&apos;s licensee for the United States, Canada, and Mexico. Design of this installation is essentially the same as the German original, but provision was made for varying the method to adapt the process to specific objectives of American portland cement production. Differences between German and American cement clinker production practices are directly related to differences in three primary production cost items: fuel, labor, and power. Because fuel costs are high in Germany and elsewhere in Europe, thermal efficiency has been the first objective of European cement producers and manufacturers of rotary kilns. The Germans have developed such recuperative equipment as the present suspension preheater, the Miag calcinator, and the Lepol kiln, the invention of 0. G. Lellep. In North America labor is the principal cost item, although rising fuel costs are of growing concern. High clinker production is therefore of first importance. Recent installations of longer dry process cement kilns have been disappointing, failing to make satisfactory reductions in exit gas temperatures when production is held at an acceptable level. The Humboldt suspension preheater satisfies both

Jan 1, 1955

By S. Suphi Yavasca, A. M. Gaudin

THIS paper is intended as a contribution to our knowledge of the mechanism of comminution and of the work of crushing. In a previous paper&apos; it was shown that with quartz comminution proceeds as follows I. The size distribution of broken fragments made by a single fracture is such that the new surface on each grade is the same. 2. Multiple fracturing results in a size distribution such that in the fine sizes the surface per grade is the same in every grade; in coarse sizes the surface per grade decreases gradually with increasing size. In that paper it was mentioned that determinations on minerals other than quartz were in course of completion in order to establish the generality of these observations. In this paper, condensed data2 are presented for galena, pyrite and glass. Galena and pyrite are crystalline material and glass is noncrystalline. Galena has excellent cubic cleavage. Pyrite, although cubical, does not have marked cleavage. Quartz, on which the original determinations were made, does not cleave and although crystalline (hexagonal) breaks conchoidally. Glass breaks much like quartz. It is apparent, therefore, that the minerals selected represent some range in character of the solid without covering all possible types. GLASS Fifteen glass marbles were crushed individually in the pendulum crusher described in the preceding paper,1 then subjected to careful screening for 30 min. Six sized fractions were selected and cleaned in a hot 0.12 N solution of hydrochloric acid, washed with distilled water and dried on a hot plate. This was followed by an examination with a binocular microscope, to remove foreign matters not eliminated in cleaning as well as to eliminate "compacts" of fine particles. These compacts are groups of fine iragments that seem to be mechanically stuck together as a result of localized compacting during the comminution operation. The presence and the abundance of these compacts may be related to the amount and direction of the forces applied in different crushing devices. Since, properly, such compacts should be entirely eliminated in the sizing analyses, it is necessary to remove them to the last before making surface determinations on sized fractions. For example, with a - 28 + 35-mesh glass the surface areas of two samples, one cleaned with acid and under the binocular, the other only washed, were 102 and 172 sq. cm. per gram, respectively. Examination of the samples under an Ultropak microscope showed that washing alone failed to remove the compacts and also that it fails to remove certain fine dusts attached to the particles. Cleaning with acid loosens the fine dusts and

Jan 1, 1945

By David V. Ragone, Richard E. Balzhiser

The liquidus uranium concentration in the U-Bi system is given by the following expression for the temperature range 400° to 800°C: No break was observed in the curve over this temperature range. The partial molar enthalpy change for uranium in the liquidus reaction, UBi2— U + 2Bi, was found to equal 12,300 cal per g mole. Copper produced a continuous decrease in the liguihs uranium concentration at 600°C. The presence of copper in the solvent was observed to affect the uranium activity coefficient according to the following expression: duced no change in the liquidus combosition below 0.6 at. pct Pd. Higher palladium concentrations sharply depressed the uranium concentration. SOLUTE behavior in molten alloys has been shown to be strongly influenced by the presence of additional species. Much attention has been given to such phenomena in iron-base systems where a number of alloying elements and/or impurities are likely to be present in small but significant quantities. Frequently, the interaction of these solutes has altered their thermodynamic behavior to the extent that reaction equilibra are appreciably influenced. Consequently, much of the information available for binary behavior must be reevaluated when additional components are likely to be present. Similar interactions can be expected to occur in bismuth-base solvents. Interest in the use of bismuth solutions of uranium as reactor fuels has stimulated investigators to explore the effect of various elements on the liquidus uranium concentration. Criticality requirements necessitate close control of the uranium concentration which, at the anticipated operating temperature of 500°C, approaches saturation. Consequently, elements which suppress the liquidus concentration could produce serious reactivity problems. Since the fuel solution is cer- tain to contain additives, such as magnesium and zirconium, for corrosion inhibition as well as small concentrations of fission products and corrosion products, a better understanding of the possible interaction phenomena is mandatory. This need stimulated experimental programs at the Brookhaven National Laboratory and elsewhere to determine precisely the liquidus uranium concentration in the bismuth-rich portion of several ternary systems. Early experimental efforts were directed toward an accurate dcmtermination of the U-Bi liquidus over the temperature range from 300&apos; to 800°c. As shown in Fig. 1, the results to date exhibit considerable scatter. The investigations of Bareis,&apos; Teitel,2 Greenwood,3 and Cotterill and hon4 agreed well below 700°c. Greenwood and Teitel extended their studies to higher temperatures but failed to concur in their results. A more recent study by Schweitzer and weekss at Brookhaven National Laboratory between 300&apos; and 725°c, produced values 15 pct lower

Jan 1, 1962

By James Norman, O. C. Ralston, John Dasher

MOST mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chromite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficiation, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put in the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separations at a density of 4.0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabromethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in. size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. EARLIER WORK It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the

Jan 1, 1942

By Charles C. Hawes

DETERMINATION OF SILICA OXIDE iron ores usually are found in intimate association with silica and phosphorus compounds. Their quantitative separation and purification sometimes present difficult problems to the chemist. Silicic acids may represent various degrees of dehydration. They are exeedingly weak, but combine with metallic oxides and form some of the most stable oxides in nature, the silicates. When iron ores are treated with hydrochloric acid, they yield practically all their iron. However, apart from rare exceptions, varying amounts of insoluble residues of silica, alumina, lime, magnesia and compounds of phosphorus, sulphur, titanium, chromium and others will be left. If the oxides of silicon, aluminum and titanium are present in small quantities, the insoluble residue is generally very small, but the presence of these oxides is more usual in larger quantities. Therefore, only a special treatment can break the bond between these elements. Ore Residues Acids remove the soluble constituent of the ore, leaving the insoluble residue, which chemically is rock or gangue and must be treated accordingly. Alkali carbonates are used frequently to break up the residue, but other fluxes have also been recommended, such as a number of lead and boron salts. The introduction 0f these salts, which offers certain advantages, requires, however, their removal before the other constituents can be analyzed, and this elimination is sometimes difficult. Usually in quantitative analysis silicates are dissociated by fusing them in a platinum crucible with sodium carbonate, thereby forming sodium silicate, Na2SiO3, sodium aluminate, Na2Al204, sodium titanate, Na2TiO3, and carbonates of other elements. All the carbonates are soluble in hydrochloric acid, but also some silicic acid is formed that must be rendered insoluble. To this end the solution is evaporated several times, as the first evaporation still leaves as much as 5 per cent of the silica soluble. Even after a number of evaporations, minute quantities of silica may be found with the iron and alumina present. Perchloric Acid as an Agent for Dehydrating Silicic Acid Perchloric acid, HC104, (60 per cent), has been used for years as a solvent, but few chemists have used it to dehydrate silica. It is derived from anhydrous perchloric C1207, which is most unstable and dangerous. Perchloric acid is a strong oxidizing agent, which boils at 203°C. It is more effective in rendering silica insoluble than any other known agent, and most rapid in action. After perchloric acid is added to a mixture containing silicic acid, the resultant solution is

Jan 1, 1945

By W. D. Robertson

The effect of a tensile stress in accelerating the corrosion-cracking of certain alloys of aluminum, magnesium and iron is widely recognized. The literature is extensive and it is only necessary to cite the recent ASTM—AIME Symposium,l There are, however, no experimental data conclusively showing the effect of an applied compres-sive stress. It has been inferred, from the generally accepted mechanism postulated for the acceleration of corrosion by an applied tensile stress, that a compressive stress would inhibit corrosion. Furthermore, it is observed that corrosion cracks invariably start on the tension side of a specimen bent as a simple beam. This observation has led to the suggestion that shot-peening of the surface would inhibit or eliminate stress-corrosion cracking in magnesium alloys and aluminum alloys. However, the degree of inhibition produced by shot-peening does not appear in the literature except for the above qualitative references which are unsupported by experimental data. Moreover, while peening undoubtedly imposes a surface compressive stress, the alteration of the surface by the severe cold-working involved complicates the interpretation of the results with respect to the effect of a compressive stress alone. If corrosion proceeds along preferential paths produced by precipitation from solid solution, it is easily understood how a component of tensile stress normal to these paths will accelerate the corrosion and lead to ultimate failure. On the other hand, if the metallurgical conditions are such as to create preferential corrosion paths, then it is difficult to understand how a compressive Stress, produced by shot-~eening Or any other method, can inhibit corrosion except in the sense that the accelerating factor is removed. Thus, if the basic corrosion mechanism remains unaltered, there should be little or no inhibition resulting from the application of a compressive stress if inhibition is defined as the reduction of the degree of corrosion below that experienced in the unstressed state. The experiment described below was performed to isolate and evaluate the effect of a compressive stress on the corrosion and stress-corrosion cracking of a high strength aluminum alloy (24-S); and, by a Comparison of the corrosion rate of &apos;pecimens subjected to an applied tensile stress, compressive stress and in the unstressed state, to clarify the role of stress in intergranular corrosion. Experimental Procedure The experiment was conducted with the aluminum-copper-magnesium alloy known as Duralumin 24-S.* Specimens, 0.064-in. thick, in the form of I-in. wide strips sheared parallel to the rolling direction,

Jan 1, 1949

By Howard N. Eavenson

One who has been trained in belief in the law of supply and demand and its effect upon prices finds it difficult to adjust himself to the minute regulations imposed by the New Deal, and also to the bewildering changes of government policy as expressed within a short period of time between the antitrust laws and the N.R.A., and later by the Bituminous Coal Conservation Act of 1935. A survey of the coal industry since the World War, both in this country and Great Britain, however, shows that regulation of some sort is needed if any stabilization is to be achieved and if the wage structure and economic welfare of the many communities dependent solely upon coal are to be maintained. Let us look at what has happened to the industry since 1920, which can be considered as the end of the period affected by the war influence. This discussion will be confined solely to bituminous coal, although many of the general conditions are equally applicable to anthracite, the position of which now is at least as bad as that of the softer variety. Since 1920—to the end of 1934—the production of coal has decreased from 568.7 million to 358.4 million tons, or 37 per cent; the number of mines from 14,766 to 6,258, or 58 per cent; the average annual production per mine has changed from 38,512 to 57,425 tons, or 50 per cent. The number of large mines has increased considerably, and the number of men employed has decreased from 639,547 to 458,011, a reduction of 28 per cent, while the average output per employee has changed from 4.0 to 4.4 tons, or an increase of 10 per cent. The average price per ton of coal at the mine has varied from $3.75 to $1.75. During that time wages decreased largely until 1933 and since that time have increased, until now the rates paid are considerably above those in other occupations, although the actual yearly earnings are low, because of part-time work. From 1920 to the signing of the Jacksonville wage agreement in 1924, about two-thirds of the men were union members and practically all of the nonunion mines were south of the Ohio River; with the fixing of the high wage scale of that agreement, which soon proved to be an uneconomic one, many of the mines found that they could not retain their business, so gradually changed to nonunion. By 1928 the proportion

Jan 1, 1936