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By Hans Allenius, R. T. Hukki

This paper describes in quantitative terms the effect of sharpness of classification on the performance of the closed grinding circuit. The analysis is based on a large number of laboratory experiments designed to simulate the two most common industrial closed grinding systems. The experimental results show quantitatively the degree of improvement achievable by more efficient classification. In an earlier paper1 the senior author has presented a trend showing qualitative analysis of mill and classifier performance in tile closed grinding circuit. According to this analysis, the master key to a major improvement appeared to be effective removal of finished fine material from the classifier sands, or in other words, improved sharpness of classification, leading simultaneously to a substantial reduction of the circulating load. One purpose of this paper is to present the results of a quantitative investigation of the closed grinding circuit. Another is to set forth the essential pertinent variables revealed by the quantitative experiments carried out by the junior author. In the two most common systems of closed-circuit grinding, (1) feed to the circuit is introduced into the grinding unit, normally the ball mill, operating in closed circuit with the classifier; or (2) feed to the grinding circuit is introduced into the primary grinding unit, normally the rod mill, discharging into the classifier in closed circuit with the secondary grinding unit, normally the ball mill. In the following discussion, these two systems are analyzed separately in the indicated order. BALL MILL - CLASSIFIER CIRCUIT The Test Apparatus and Procedure: The test appara- tus included: (1) a F 195 mm x 220 mm laboratory ball mill rotated at a speed 77% of the theoretical critical speed, and a 7-kg batch of F 20 mm-F 50 mm steel balls; (2) a conventional 65-mesh test sieve and a Ro-Tap sieve shaker serving as a classifier; and (3) a Permaran instrument manufactured by Outo-kumpu Co. for surface area determinations by the permeability method. As no continuous closed-circuit experiments could be brought about on a laboratory scale, the process was broken down into alternating grinding and sizing steps in such a way that the new feed plus the returning sands always formed a batch of 1000 gm. For each selected grinding period and for each selected sharpness of classification the basic steps were repeated six times. Steady-state conditions were then reached. Crystalline vein quartz was used as a test material. Feed to the process consisted of -10-mesh fraction of this quartz crushed in rolls. This fraction included 15% of-65-mesh material. Experimental Results: The general flowsheet is shown in Fig. 1. Table I gives the essential data obtained representing steady-state conditions under the indicated set of variables. The table is based on 110 grinding experiments, 440 screen analyses and an equal number of specific surface area determinations. Fig. 2 shows the relationship between the cumulative net energy consumption and the cumulative number of mill rotations as evaluated by separate experiments. Note that this relationship is not linear but is instead represented by a slight curve. The data given in Table I are presented in graphical form as follows: Fig. 3 shows the produced -65-mesh material in grams per minute vs. time of grinding in minutes; the sharpnesses of classification at 65 mesh were 100%, 75% and 50%. It is clearly indicated that the highest-capacity figures call for relatively short grinding times and for the sharpest possible classification. Fig. 4 presents the specific surface area on the final -65-mesh product in square centimeters per gm vs. time of grinding in minutes. In conventional mineral dressing processes, a final product characterized

Jan 1, 1969

Meeting of Apr. 23, 1915.-The Iron and Steel Committee was authorized in its discretion to defer the date of acceptance of papers for the Hadfield Research Prize to Nov. 1, 1916. The sum of $250 was appropriated as a guarantee fund to establish a Library Research Bureau in co-operation with the other Founder Societies. The sum of $50 was appropriated to the Puget Sound Section. The sum of $250 was appropriated to the San Francisco Section. The sum of $125 was appropriated to the St. Louis Section. The matter of memorializing the New York State Constitutional Convention was referred to the New York Section of the Institute with authority to act as a Section only. Upon recommendation of the Committee on Membership, 50 Mem¬bers, 1 Associate, and 6 Junior Members were elected.

Jan 6, 1915

CHARLES G. ROEBLING Charles Gustavus Roebling, president of the John A. Roebling's Sons' Co., of Trenton and Roebling, N. J., and of the New Jersey Wire Cloth Co., of Trenton, and vice-president of the John A. Roebling's Sons' Co., of New York, died at his home, No. 333 West State Street, Trenton, on Oct. 5, 1918. Mr. Roebling, who was born in Trenton, was a son of the John A. Roebling who finished the plans for the Brooklyn Bridge just before he died. The bridge was completed by his sons, Charles G. Roebling and Col. Washington A. Roebling. Upon graduation from the Rensselaer Polytechnic Institute in 1871, Charles Roebling became associated with the Roebling company as a mechanical engineer. He was engineer and builder of the suspension

Jan 12, 1918

Organization Place Date 1917 American Society of Sanitary Engineers Grand Rapids, Mich. Aug. 1-3 National Association of Stationary Engineers... Evansville, Ind. Sept. 10-15 National Safety Council New York City. Sept. 10-15 National Exposition of Safety and Sanitation. New York City Sept. 10-15 American Iron, Steel & Electrical Engineers..:. Philadelphia, Pa. Sept. 10-14 American Institute of Metals Boston, Mass. Sept. 24-29 American Foundrymen's Association Boston, Mass. Sept. 24-29 Chemical Industries, Third National Exhibition. New York City Sept. 24-29

Jan 8, 1917

By Carl Thieme

INDUSTRIAL specialization has rapidly created a demand for new and better alloys. A more thorough understanding of the requirements of specific industries and the discovery of processes by which it has been made possible to utilize certain metallic elements in larger quantities, together with greater purity in most virgin metals, has resulted in a great increase in the number and variety of alloys. This increase in the number of elements entering into non-ferrous alloy manufacture has increased the contamination in secondary metals, as received by the smelter. In order to successfully refine scrap of a much more complex nature it has been necessary for the smelter to install new equipment and to constantly search for new methods of refining as well as to improve the methods already in use. In some instances it is largely responsible for specialization in the secondary metal industry. It is usually necessary to remove the contaminating impurities in scrap or eliminate to a degree not objectionable, no matter how introduced. In order to know what metals or elements are of an objectionable nature, the smelter must make a study of the effect of single elements and combinations of elements on many of the physical and mechanical properties, such as strength, ductility, color, hardness, casting soundness, etc. The smelter of secondary metals must be able to utilize scrap materials of all kinds, for, sooner or later, most fabricated metal parts and the waste products formed during the process of manufacture find their way to the smelter. In addition, the smelter, in contracting for salvaged material from the producer, gets some undesirable and unusual materials. The value of secondary metals and the importance of their recovery has increased in recent years and it is no longer sufficient to recover the base metal only, such as copper from copper-bearing material, but it is essential that other elements present be recovered and converted into useful form.

Jan 1, 1928

By H. H

This paper describes the milling practice and operating results of the recently installed heavy-media separation plant of Barton Mines Corporation, the world's largest producer of garnet. This pioneer application of heavy-media separation (sink-float) processes for the beneficiation of a nonmetallic ore is unique in many respects, the details of which will be apparent from the following presentation. Characteristics of the Ore The property is on Gore Mountain, 5 miles west of the village of North Creek, New York, and 11 miles by road. The altitude of the mine is approximately 2800 feet. The valuable mineral, garnet, occurs in a surface deposit, the ore body being about ¾, mile long and varying in width from 50 to 300 ft. The garnet, principally almandite, Fe3Al2 (SiO4)3, occurs in a metamorphic rock of uncertain origin. The gangue mineral is principally hornblende, which constitutes from 40 to 80 per cent of the rock. The remainder of the gangue is divided between plagioclase feldspars and hypersthene, with smaller amounts of biotite, apatite and pyrite. The garnet content of the ore body varies from 5 to 20 per cent of the mass and averages about 10 to I2 per cent. The garnet occurs as crystals, mostly imperfectly developed, known locally as "pockets." These crys- tals vary in size from a fraction of an inch to a foot or more in diameter. Occasionally crystals have been found up to 30 and 36 in. in diameter but they average 4 to 6 inches. Nearly every crystal of garnet is surrounded by a rim of coarsely crystalline hornblende. The quarry faces are striking in appearance, showing crimson-red garnet crystals with their coal black rims scattered over a grayish black background. The specific gravity of the garnet is 3.8 to 4.1 while that of the hornblende ordinarily is 3-07 to 3.24. Some specimens of very dense hornblende have been found with a specific gravity as high as 3.40. The garnet crystals are laminated in structure, and readily cleave into flat, tabular pieces with sharp, chisel-like edges. Even when crushed to a very fine size, the garnet retains this flat, sharp, slivery grain shape. This characteristic, together with its hardness and toughness, gives it its value as an abrasive- Former Operations Mining operations have been carried on for 60 years. Until 1923, only the oxidized (soft rock) section of the ore body was mined. The oxidation, which affected the garnet only slightly, made possible the removal of the garnet from the rock by hand after it was blasted down, using small hand picks. In 1923 a mill was erected on the property, and was rebuilt and redesigned in 1928. Before the adoption of heavy-media separation, concentration was effected by

Jan 1, 1943

By H. H

This paper describes the milling practice and operating results of the recently installed heavy-media separation plant of Barton Mines Corporation, the world's largest producer of garnet. This pioneer application of heavy-media separation (sink-float) processes for the beneficiation of a nonmetallic ore is unique in many respects, the details of which will be apparent from the following presentation. Characteristics of the Ore The property is on Gore Mountain, 5 miles west of the village of North Creek, New York, and 11 miles by road. The altitude of the mine is approximately 2800 feet. The valuable mineral, garnet, occurs in a surface deposit, the ore body being about ¾, mile long and varying in width from 50 to 300 ft. The garnet, principally almandite, Fe3Al2 (SiO4)3, occurs in a metamorphic rock of uncertain origin. The gangue mineral is principally hornblende, which constitutes from 40 to 80 per cent of the rock. The remainder of the gangue is divided between plagioclase feldspars and hypersthene, with smaller amounts of biotite, apatite and pyrite. The garnet content of the ore body varies from 5 to 20 per cent of the mass and averages about 10 to I2 per cent. The garnet occurs as crystals, mostly imperfectly developed, known locally as "pockets." These crys- tals vary in size from a fraction of an inch to a foot or more in diameter. Occasionally crystals have been found up to 30 and 36 in. in diameter but they average 4 to 6 inches. Nearly every crystal of garnet is surrounded by a rim of coarsely crystalline hornblende. The quarry faces are striking in appearance, showing crimson-red garnet crystals with their coal black rims scattered over a grayish black background. The specific gravity of the garnet is 3.8 to 4.1 while that of the hornblende ordinarily is 3-07 to 3.24. Some specimens of very dense hornblende have been found with a specific gravity as high as 3.40. The garnet crystals are laminated in structure, and readily cleave into flat, tabular pieces with sharp, chisel-like edges. Even when crushed to a very fine size, the garnet retains this flat, sharp, slivery grain shape. This characteristic, together with its hardness and toughness, gives it its value as an abrasive- Former Operations Mining operations have been carried on for 60 years. Until 1923, only the oxidized (soft rock) section of the ore body was mined. The oxidation, which affected the garnet only slightly, made possible the removal of the garnet from the rock by hand after it was blasted down, using small hand picks. In 1923 a mill was erected on the property, and was rebuilt and redesigned in 1928. Before the adoption of heavy-media separation, concentration was effected by

Jan 1, 1943

By Carl Thieme

INDUSTRIAL specialization has rapidly created a demand for new and better alloys. A more thorough understanding of the requirements of specific industries and the discovery of processes by which it has been made possible to utilize certain metallic elements in larger quantities, together with greater purity in most virgin metals, has resulted in a great increase in the number and variety of alloys. This increase in the number of elements entering into non-ferrous alloy manufacture has increased the contamination in secondary metals, as received by the smelter. In order to successfully refine scrap of a much more complex nature it has been necessary for the smelter to install new equipment and to constantly search for new methods of refining as well as to improve the methods already in use. In some instances it is largely responsible for specialization in the secondary metal industry. It is usually necessary to remove the contaminating impurities in scrap or eliminate to a degree not objectionable, no matter how introduced. In order to know what metals or elements are of an objectionable nature, the smelter must make a study of the effect of single elements and combinations of elements on many of the physical and mechanical properties, such as strength, ductility, color, hardness, casting soundness, etc. The smelter of secondary metals must be able to utilize scrap materials of all kinds, for, sooner or later, most fabricated metal parts and the waste products formed during the process of manufacture find their way to the smelter. In addition, the smelter, in contracting for salvaged material from the producer, gets some undesirable and unusual materials. The value of secondary metals and the importance of their recovery has increased in recent years and it is no longer sufficient to recover the base metal only, such as copper from copper-bearing material, but it inessential that other elements present be recovered and converted into useful form.

Jan 1, 1928

By G. P. Marino

The "conductivity ", Kr, of a spherical void in a linear temperature gradient due to radiation is calculated by integration of the general expression for diffuse radiation between two gray surfaces of arbitrary orientation. The spherical geometry allows an exact evaluation of the phenomenon without resorting to up-proximate expressions for the radiant heat flux. The resulting expression for Kr is three quarters of the approximate value obtained by Loeb. IN the determination of the thermal conductivity of porous materials such as sintered UO2 and ThO2 fuel pellets, the magnitude of the thermal conductivity in the pores due to radiative heat transfer across the pore, Kr, may be important in assessing the total conductivity of the pellets. Loeb' has calculated Kr for various pore geometries by approximating the net flux of heat between two surfaces of temperature difference AT as 4eT~AT and obtained: K,=4yoet3odp [1] where a is the Stefan-Boltzmann constant, E is the emissivity of the radiating surface, To is the average absolute temperature of the region across which radiation occurs, dp is the largest dimension of the gap in the direction of heat flow, and y is a geometric factor. That is: y = 1 for laminar pores and cylindrical pores with axes parallel to the heat flow direction, y = 2/3 for spherical pores, y = /4 for cylindrical pores with axes perpendicular to heat flow direction. It was the purpose of this work to obtain an exact expression for K, in spherical pores by integration of the general expression for the net heat transfer between two incremental areas on the surface of a spherical pore. This procedure yields a value of Kr 3/4 of that obtained by Loeb. I) CALCULATION OF Kr Fig. 1 illustrates the general geometry which defines the problem. The total emissive power for a gray body is given by: E = EoT4 [2] where E is the radiated energy per unit area of the radiation surface per unit time, T is the absolute temperature, o is the Stefan-Boltzmann constant (o = 5.67 X lo- '' watt per sq cm-"K1), and E is the emissivity of the surface. Although Eq. [2] gives the exact expression for the total emissive power of any gray body, all practical problems involve the net exchange of thermal radiation between a body and surrounding bodies. The two major considerations in the solution of such problems are a) shape and relative position of the surfaces and b) the emissivities of the surfaces. In this work it shall be assumed that all incremental areas on a pore have the same emissivity and, further, that little or no reflection occurs (i.e., the radiation hitting a surface is either absorbed or transmitted). Thus, the solution of the stated problem requires only that consideration a be satisfied. Consider two incremental surface areas dA 1 and dA2 of the same material in a general orientation to one another. Let dAl be at temperature TI and dAz be at T2. Fig. 2 illustrates the geometrical parameters involved. That is, 71, is the normal of dA, n2 the normal of dA2, r the line connecting the centers of each area, 81 the angle between nl and r, and Q2 the angle between 7,2 and r. Using Eq. [2] and the Lambert cosine law of diffuse radiation it is easily shown that:293 WdAf- dA, = ecr T*------^fpi------" dAidA2 [ 3a 1 and

Jan 1, 1970

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

By Albert A. Mathews

OUTCROPS of gypsum rock near the present site of the city of Gland Rapids, Mich., were known to fur traders early in the nineteenth century. However, the deposits seemed without value and were not worked for some time. So far as cat1 be learned, Michigan gyp- sum was first used by a plasterer who settled in Grand Rapids in 1834 as a member of its fourteenth white family. In building a house for one of the early traders, be used some otnamental stucco mouldings manufactured from the local gypsum deposits for decorations in the gables and around some circular windows. The gypsum was broken out with a hammer, ground in an Indian corn mill, and burlled in a caulclron kettle,. After two attempts, the ornaments were successfully set, and remained on the house until it was destroyed by fire in 1850.

Jan 1, 1936

By Clarence P. Linville

(Pittsburg Meeting, March, 1910.) IT is recognized that, in all metallurgical operations, the greatest possible uniformity in all conditions is essential to the best results. It is the constant aim of metallurgists to secure this uniformity, and their success in this respect has been in many cases the cause of great advances in the metallurgical processes themselves. Of all such processes, the production of pig-iron in the modern blast-furnace is perhaps the most complex and the most difficult of control. Notwithstanding the great progress of recent years, there is still great difficulty in obtaining anything like uniform conditions and results in the manufacture of pig-iron. The reason is not far to seek. The ores vary in composition and physical properties, often carrying a varying amount of gangue material, unevenly distributed The coke may vary in composition, cell-structure, moisture, hardness, and other properties. The blast, the weight of which far exceeds that of any other constituent, varies in its moisture-content and consequently in its chemical composition ; and its temperature, by reason of the method of heating, is not uniform, but, besides varying from time to time with atmospheric and other outside conditions, has a maximum and minimum for every changing of stoves. Now, with regard to these variations, the modern demand for uniformity has been greatly aided. Chemical analysis has made it possible to select ores so that the composition of the charge can be kept fairly constant; coal may be obtained from a given field, and coked in the same kind of ovens under conditions which . make the fuel practically uniform ; the Gayley

Mar 1, 1910

By Pedro G. Salom

I HAVE had an opportonity, within the last few months, of making a large number of physical and chemical tests of steel for boiler and ship-plate, which has been, and is now being, used principally for the United States Government cruisers, now building in Mr. John Roach's yard, at Chester, Pa. Through the courtesy of the Messrs. Houston, of the Chester Rolling Mills, I have the honor to lay before the members of the Institate the results of these tests. These results have developed some points in regard to the nature of steel, which are more or less new, and which, I hope, will prove interesting. The original specifications, as regards the manner of testing, were so inipracticable (when their severity mas taken into consideration), that the keel of the first vessel, which will be launched next month, would, had they been carried out, probably not have been laid until next year. At my suggestion, in order to simplify and expedite the immense amount of testing that had to be done, the Naval Advisory Board was induced, after considerable discussion, to alter the specifications, so as to test each heat, instead of each lot of twenty plates, but reserved the right of making the quenching-test on a piece from each ingot, after it had been rolled. This relieved us from the anxiety of having a lot of plates rejected, after they had beell rolled and sheared, by reason of the presence of one or two plates which might have been injured in heating or rolling, or which might not have been able to stand the tests; while it insured the Government in obtaining a uniform quality of steel, and prevented the temptation to introduce a half-dozen or more had plates in a lot, and run the risk of their being selected as the testplates. I give below a portion of the original specifications, as prescribed

Jan 1, 1884

By R. L. Pober, L. Kaufman, E. V. Clougherty

Composite structure of hafnium, zirconium, and titanium diboride with additions of metals and/or compound phases were prepared by reactive high-pressure hot pvessing and evaluated in air and in mixtures of oxygen and helium at temperatures up to 2400°K and at linear flow rates of 0.1 to 0.2 ft per sec stp. Oxidation characteristics, principally depth of conversion of diboride to dioxide, were determined by a gas analysis method and by postoxidation metallo-graphic analyses. The best oxidation resistance was observed for hafnium diboride-silicon carbide composite which exhibited a 6-mil conversion to dioxide for a 1-hv oxidation in air at 2200°K compared to a 20-mil recession for hafnium diboride with no additive. Analogous improvements in oxidation resistance were observed for the addition of silicon carbide to zirconium. EARLIER investigationof the oxidation behavior of the diborides of the transition elements of Groups IVA and VA in flowing gas mixtures have produced a ranking of these compounds according to which HfB2 is the most oxidation-resistant followed in turn by ZrB2 > TiB2 > TaBz > NbB2. Other ~tudies~-~ have examined the physical, thermal, and thermodynamic properties of these diborides to provide a sound basis for the more detailed and specialized investigations which are required to generate the information needed to assess the usefulness of such materials in high-temperature oxidizing environments. Recent oxidation studies7 have examined the effect of variations of metal and boron content on the oxidation characteristics of zirconium and hafnium diboride in flowing gas mixtures including air and helium plus oxygen. Results obtained in the latter investigation confirmed the superior oxidation resistance of HfB2 over ZrB2. Moreover, metal-rich compositions of hafnium diboride showed improved oxidation resistance over boron-rich compositions at temperatures up to 2000°K; at higher temperatures the differences are not distinguishable. In particular HfBI.7 exhibited a diboride to dioxide conversion depth of 4 mils in 1 hr at 2000°K; HfB2. 2 exhibited a conversion depth of 16 mils for the same exposure.~ Specimens for the study of metal and boron stoichiometry on the oxidation characteristics of HfB2 and ZrB2 were prepared by high-pressure hot pressing, a specialized type of fabrication which produced dense crack-free bodies of the desired compositions with no significant impurity introductions. The purpose of the present investigation was to explore the possibility of further improving the oxidation resistance of the metal-rich ZrB, and HfB2. The plan to accomplish this objective was based in the formulation of several diboride compositions containing other compounds and phases which are generally known to have good oxidation resistance in one or more types of test environment. Ideally, such additives would also enhance or at least not diminish other boride property values principally mechanical strength and those parameters related to thermal stress resistance. The additions selected for HfBz included zirconium, aluminum, and (Ta + TaB2) designed to produce ternary metal diborides, hafnium to form a discrete HfB phase, chromium to provide a metal skeletal phase, (Hf + Si) to form a discrete hafnium silicide phase, and Sic to provide a discrete second phase. Additions to ZrB2 included A1 + B designed to produce a ternary metal diboride, Zr + Si to form a discrete zirconium silicide phase, and Sic to provide a discrete second phase. All the specimens were prepared by high-pressure hot pressing which was used to advantage to fabricate billets of the variety of compositions desired and suitable for oxidation testing. The present investigation also included the evaluation of high-pressure hot-pressed TiB2and TiB2-20 vol pct Sic, conventionally hot-pressed Boride 2,' and KT silicon carbide. Boride

Jan 1, 1969

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By C. S. Smith, L. H. Beck

KNOWLEDGE of the Cu-Zn constitution diagram was critically examined in 1944 by G. V. Ray-nor,1 who suggested the diagram reproduced in Fig. 1 as the best evaluation of available data. No pertinent work on the constitution has been published since that time, although a number of authors have discussed transformation kinetics and theory. Despite the large amount of work that has been done on the constitution of these industrially important and scientifically interesting alloys, minor uncertainties still exist. For example, it is still not possible to say definitely whether a two-phase region exists between the ordered and disordered forms of the 8 phase. A careful re-examination of the phase boundaries in this part of the diagram was therefore undertaken. Two methods were selected for the new investigation—quantitative metallography for the higher temperatures and precision lattice parameter measurement for lower temperatures. Because of the relatively narrow two-phase regions flanking the ß phase in these alloys, quantitative metallography is particularly suited for their examination, since the relative amounts of the two phases are very sensitive to their compositions. The method, however, is useless below about 350°C because of the inadequate resolution of the two constituents. Below 400°, however, the X-ray diffraction method is applicable, although it is of somewhat lower sensitivity in this system. The changes of composition that occur during quenching from above about 500°C entirely vitiate X-ray measurements at room temperature though they do not affect metallographic area measurements. The two methods overlap and supplement each other admirably. Both methods depend on the attainment of equilibrium composition of the two phases in a more or less intimate mixture and thus avoid the difficult problems of nucleation and long range diffusion involved in the conventional metallographic bracketing method. The alloys were melted from a master alloy made from re-electrolyzed cathode copper and Horsehead 99.99 pct Zn. Melting was done under a cover of either borax or charcoal and the alloys cast into a 7/8 in. sq graphite mold for the a-ß alloys or a 3/8 in. diam cylindrical graphite mold for the ß-? alloys. The a-ß alloys were rolled at 750°C to 5/8 in. sq; annealed for 24 hr at 800°C and quenched; then rolled and swaged at 200°C to 3/8 in. diam rods, annealed 24 hr at 200°C, quenched and cold rolled 2 pct reduction. This treatment was intended to obtain a small grain size and to produce many nuclei of the minor phase for growth on subsequent heat treatment. The unworkable ß-? alloys were given preliminary treatment by sealing in Vycor tubes in vacuum and annealing for 4 hr at 800°C followed by cooling in air. Samples of homogenized alloys were checked spectrographically for impurities, but the principal components were determined on samples subsequent to heat treatment. The impurities analyzed averaged approximately as follows: Ag, 0.0002 pct; Fe, 0.004; Si, 0.0008; Cd, 0.005; Mg, 0.0002; and Pb, 0.002. For metallography, samples of appropriate composition were cut into rods 5/8 in. long, sealed in pyrex tubes in vacuum and annealed for eight weeks at temperatures of 470°C and below, two weeks at 480°, 500°, and 600°C, and 4 hr at 700°C, followed by quenching in cold water. Temperatures were accurate to ±2°C. The cylinders were then machined to 8.7 mm diam and a slice weighing 1.5 g cut with a thin saw transversely from the center of each. This

Jan 1, 1953

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,' published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By R. W. Shoenberger, J. A. Grina, R. J. VanPelt

The many alternatives open to coke plant operators for improving overall coke quality and strength are discussed in this paper. Programs undertaken by US Steel research and coal operations during the previous ten years to improve coke strength are described. New techniques in use, or being considered for future use, are also discussed.

Jan 1, 1982

By Ernest Stütz

(New York Meeting, October, 1918.) THE problem of increasing blast: furnace efficiency through diminution of flue-dust production while operating with burdens consisting largely of fine ores has of recent years attracted the attention of metallurgists, whether directly or indirectly interested in the economies of iron smelting, and the various methods evolved from theory or practice have been submitted to wide discussion. After the very thorough and, at that time, exhaustive view of the whole subject, which was afforded to the industry by the meeting of this Institute in February, 1912, the subject was again taken up at the meeting of the Verein deutscher Eisenhüttenleute at Diisseldorf in December, 1912. While American and German conditions are not entirely identical, it may be of interest to give here the words of the gentleman summing up the discussion at the Diisseldorf meeting: ' The chief advantage offered by the use of briquettes lies in the fact that disturbances in the furnace, caused mostly by the presence of fine ores in the burden, are avoided, and that blast pressure can be considerably reduced. The resulting economies cannot be overrated, as, with lower blast consumption per ton of product, the installation will be able to take care of increased production. In consequence of lower pressure and speed of blast, heat is more efficiently utilized, flue gas temperature is lowered, and coke particles are less liable to be carried along with the flue dust, of which considerably less is produced. Finally, by increased regularity of operation and higher . temperature in the lower parts of the furnace, the quality of the product is improved. The question of briquetting iron ores has grown to be one of the most important in the iron industry, and, it is not any more a question of what is the cost of briquetting ton of ore, but what, in using ore briquettes, is the cost of production of a ton of iron.'

Jan 7, 1913

By EVERETTE DE GOLYER

USE of geophysical methods in the search for new pools and as an aid in the development of known pools and prospects reached a new all-time peak for the oil industry in 1933. The outlook for 1934 is for work to continue at an even greater rate. The area of greatest activity, as in previous years, was in the Gulf coastal plain of Texas and Louisiana, particularly through a belt of territory some 20 to 30 miles wide parallel to the coast line and some 80 miles inland from it-the so-called "Jackson play" or "Conroe trend." This area was surveyed in an attempt to find additional pools of a type similar to Conroe, a pool not discovered directly as a result of geophysical surveys but one which was indicated by refraction surveys before it was drilled and one which was accurately outlined as to structure by reflection surveys shortly after the completion of the first few wells. Surveys were made over this belt, extending from Texas, across Louisiana and into Mississippi and Alabama, chiefly by the reflection method and torsion balance, and to some extent by pendulum and magnetic methods.

Jan 1, 1934