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By C. E. Birchenall, R. H. Condit

THREE surface activity procedures are in com--L mon use for the determination of diffusion coefficients in solids. In the oldest of these' the activity observed at the original surface is compared before and after diffusion, where all the activity is in a thin, plated layer on the surface before diffusion. Partial absorption of the radiations from active atoms which have diffused below the surface reduces the effective activity after diffusion. The formula employed to calculate the diffusion coefficient is where F, is the ratio of final to initial activity at the surface, measured with identical counting geometry; Z=u3Dt, where D is the diffusion coefficient; t is the diffusion time; and u is the absorption coefficient for the radiation in the solid as defined by Lambert's law. This absorption law implies that all the rays are parallel to each other and normal to the specimen surface. This assumption of a collimated beam used by Steigman, Shockley, and Nix has been adopted by all other investigators and, although it gives results which are approximately correct under restricted physical conditions, it does not represent many actual circumstances. It is the purpose of this paper to show the importance of the divergent rays and to indicate a procedure for taking them into account. In the residual activity method the activity is determined on a series of surfaces ground on the specimen at progressively greater depths in the diffusion layer parallel to the initial surface. Gruzin2 has de- rived a formula for this procedure, which may be put in the form where I is the ratio of the activity measured at a newly ground surface at distance k below the initial surface to the activity at the initial surface measured after diffusion, and K= k/2p Dt. A third procedure involves the autoradio-graphic determination of activity on a plane ground at a small angle to the initial interface through the penetration zone. Aut oradiography can be particularly sensitive to the oblique rays. Unlike most counters which detect essentially all ß particles or X-rays which enter the active volume as a single event, the photographic emulsion may be thin enough so that oblique rays with longer path length in the emulsion produce more darkening than rays which move normal to the film plane. Consider a plane containing a source of radiation uniformly spread over a circle and a point counter located on the perpendicular through the center of the circle. As the counter moves along this line, the total angle 6, at the counter subtended by the specimen will vary. For a fixed counter distance, let 6 be angle between the counter axis and the line connecting the counter to a point P on the active plane. If an absorber of thickness X is interposed parallel to the source between counter and source, the ray from point P to the counter will pass through an absorber thickness X secant 6. Exponential absorption is assumed to hold for all rays. If r, is the ratio of intensity at the counter with absorber to the intensity without absorber and a = pX, 1 00 The behavior of this integral, evaluated numerically,

Jan 1, 1957

By R. J. Keene

The South Works high-tonnage billet caster was started in late March 1971, with the first heat being successfully cast to completion. Currently, over 31,500 tons per month are being produced. U. S. Steel designed and built this caster with the objective of producing quality-steel billets for critical bar, rod, and wire applications. The essential design parameters were based on studies conducted on the Research Laboratory's pilot caster, also located at South works. 1,2,3)* The caster is a four-strand, straight-mold machine that produces 7.5-inch- square billets at rates exceeding 300 tons per hour. An in-line-reduction mill reduces each strand to either 6-inch-, 5-inch-, or 4-inch-square billets.

Jan 1, 1972

By J. B. Newkirk

IN 1939 Bitter and Kaufmann1 suggested that iron, precipitating from a copper-rich, Cu-Fe solid solution, appears initially as coherent particles of r-Fe which transform to the body-centered-cubic form of iron when the alloy is cold worked. Since then there has been considerable discussion, supported only by indirect evidence, regarding the validity of the concept. For example, Reekie, Hutchison, and Hether-ington2 interpreted the changes in electrical resistance accompanying the aging of Cu-Fe specimens in terms of a coherent 7-Fe precipitate which transformed to the incoherent a-phase during long aging or cold working. Greninger- ound that Cu-Fe alloys which had been water quenched from 1050" and then held at 650°C for 3 hr changed from weakly to strongly ferromagnetic as the aged wire was subsequently cold worked. He also found diffraction lines corresponding to body-centered-cubic iron in Debye-Scherrer patterns given by aged and worked specimens but lines corresponding to only one face-centered-cubic phase in specimens which had been aged but not worked. Knoppwost,' and later Cech and Turnbull,5 found that aged Cu-Fe specimens showed a slight increase in ferromagnet-ism after they had be? cooled in liquid nitrogen. Very recently Denney6 followed the kinetics of the precipitation reaction as indicated by the saturation magnetization, hardness, and diffuse X-ray effects. The experimental results reported by all of the authors mentioned above are readily explained in terms of the Bitter and Kaufmann concept. However, most of the evidence is indirect when used to define the structural changes involved. It was the aim of the present investigation to determine the mechanism of precipitation of iron from a Cu-Fe solid solution in the light of available published information and with additional new and more direct experimental data. Experimental Method At 1060°C copper will contain up to 3 atomic pct Fe in equilibrium solid solution.7 The solvus slopes rapidly toward lower iron concentration, so that at 600°C only about 0.5 pct Fe remains in solution at equilibrium. Below the eutectoid temperature (850°C), the iron-rich phase in equilibrium with the copper-rich solid solution consists of body-centered-cubic a-Fe. Above 850 °C the equilibrium iron-rich phase is face-centered-cubic r-Fe. The alloy to be studied was made by melting electrolytic iron and OFHC copper by induction under vacuum in an Alundum-lined crucible. The metal was held molten for about 5 min, after which time the power was turned off and the crucible was tipped about 70" to promote directional solidification. The resulting ingot, containing 2.5 wt pct Fe by analysis, was clean, large grained, and free of gross segregation. Slices % in. thick were cut from the ingot, rolled to 1/8 in. in thickness, homogenized in hydrogen at 1060°C for 24 hr and, finally, quenched in cold water. Specimens for all subsequent tests were made from these slices. Squares measuring about 1 cm on a side were cut from the slices to make specimens for studying hardness and microstructure. Wires (0.020 in.) for the Debye-Scherrer survey were drawn from 1/8 in. sq rods which had been cut from the homogenized slices. Large crystals for observing diffuse X-ray diffraction effects were prepared by mechanically

Jan 1, 1958

By Elmer W. Pehrson

Minerals have played a prominent role in the affairs of man and nations since time immemorial but with the advent of the industrial revolution, expanding use of the products of the mineral kingdom became synonymous with the material progress of mankind. Individuals and business groups have recognized this fact so have been aggressive in searching for and utilizing mineral resources, with notable success. Indeed, their achievements are primarily responsible for the present Machine Age. On the other hand, until recently the body politic has failed to grasp fully the essentiality of minerals although, at times, access to mineral supplies has been an important factor in the political maneuvers of nations. This chapter is concerned primarily with the broader political and economic relationships of mineral resources to the world economy, and with the internal and external actions of nations in the field of minerals. Many factors that condition the mineral economy of regions and the world as a whole, influence the internal and external affairs of individual nations. The more important of these are: 1. The nature of man's dependence on minerals. 2. The problems resulting from the unique characteristics of mineral occurrence. 3. Geopolitical concepts. 4. Minerals and world power. Actions of individual nations affecting their mineral economy seek two basic objectives : 1. Attainment and maintenance of prosperity. 2. Military security. Other objectives may be cited but on careful analysis they become integral parts or extreme phases of the two points noted above. For example, the twentieth century aggressions of the USSR, Germany, Italy, and Japan might be considered as direct bids for world power but they also can be interpreted as exaggerated or mistaken efforts toward military security and peacetime prosperity. Similarly, trade barriers, nationalization of industries, foreign exchange manipulations, taxation, monopolistic prac-

Jan 1, 1959

NEW MEMBERS The following list comprises the names of those-persons who became members during the month of January, 1914. Members ADIASSEWICH, ALEXANDER, Dept. of Commerce & Industry, 11, Nadejdinskaia, St. Petersburg, Russia. BEARD, JOHN W., Mine Supt., Lane-Rincon Mines, Inca, Temascaltepec, Mex., Mexico; BORCHERDT, WALTER 0., Supt The Bertha Mineral Co., Austinville, Va BREWSTER, BURT B., Sales Engr., Sullivan Machinery Co., 1127 Central National Bank Bldg., St. Louis, Mo: CHASE, ROGER E., JR., Assayer 3906 No. Baltimore St., Tacoma, Wash. CULBERT, J. VICTOR 7S4 Wellington St., London, Ont., Canada; DICKINSON, ALBERT W., Supt. Of Mines Bevier, MO. DODSON, T. M Mores, Colliery, Schuylkill Co., Pa FORREST, CHARLES N., Chem. Engr Maurer, N. J.

Jan 2, 1914

Year Institute of Metals ? Petroleum - Iron and Steel ? Coal ? Mineral Industry Education - Industrial Minerals 1918 W M CORSE 1919 1920 W H BASSETT 1921 1922 W B PRICE 1923 E DEGOLYER 1924 G K ELLIOTT 1925 F JULIUS FOHS 1926 PAUL D MERICA 1927 JOHN M LOVEJOY 1928 S SKOWRONSKI A W AMBROSE RALPH H SWEETSER 1929 J B UMPLEBY G B WATERHOLSE 1930 ZAY JEFFRIES C V MILLIKAN W J MACKENZIEHOWARD N EAVENSON 1931 SAM TOUR C E BEECHER F M BECKET 1932 C H MATHEWSON EARL OLIVER F N SPELLERTHOMAS G FEAR C H FULTON

Jan 1, 1952

By F. Weinberg

Measurements have been made of solute segregation during dendrilic growth by using radioactive solute elements and ,measuring the activity of den(12-ites cut from decanted specimens. This has been done for both lead awl tin based binary alloys contaitzing the following solute additions: Ag, T1204, was dependet on ko, the equilibrium distribution coefficient in the following way Fay k &apos;c 0.1, C/C 0.6; for k0 >0.1. 0.6 <c,/c,< I. Qualitative obse?-vations were madc of dendritic segregation, by using autoradiographic techniques, for the Sn + Ag110 and Sn + Tlo4 systems. The observation were found to he in general agreement with the measurements ofCA/Co. Autoradiographic were also obtained of scctiolccl delzr11-iie stalks. These indicated that the stalks had a substructure, dclileated by solute corzetlt?atio?zs nlolg the substructure walls. A new dendrite growth direction <JI2> is reported for tila. SOLUTE segregation in dilute binary alloys has been investigated by Pfann,&apos; Smith, Tiller, and Rut-ter,&apos; and others. They considered the case of a slowly advancing plane solid interface, and derived expressions for the distribution of solute in both solid and liquid during solidification. To determine these expressions, they assumed no diffusion in the solid and either complete mixing in the liquid:&apos; or diffusion controlled solute movements in the liquid without any convective mixing.&apos; The present investigation considers solute segregation during dendritic growth, in which case the solid-liquid interface is not plane, and the growth rates are rapid. Segregation under these growth conditions has not been treated mathematically, because of the relative complexity of the system. It has been suggested by Chalmer, on the basis of preliminary results, that an alternative to the diffusion and heat flow controlled conditions during growth is &apos;diffusionless" dendritic growth in which solid is formed with the same composition as the liquid. He suggests this type of growth may depend upon a solvent-solute relationship that permits some solid solubility without excessive increase in internal energy, as is the case for solutions of tin in lead. On the other hand, Montariol,4 and others, have shown experimentally that some segregation does occur during dendritic growth in metals using etching and radioactive tracer techniques to indicate the concentrations of the solute. The present investigation was undertaken to determine, both qualitatively and quantitatively, the extent of solute segregation associated with dendritic growth in a series of binary alloys, as a function of solute concentration. PROCEDURE The solvent materials used were Vulcan Electrolytic tin (99.997 pct purity) and Tadanac lead (99.998 pct purity). The solute materials were Zn, Sn, and Sb (better than 99.998 pct purity), Ag and Co (99.5 pct purity), and T1 (Fisher "purified" metal sticks). Activation of the solute metals was carried out in the reactor at Chalk River, Canada. Master alloys were prepared by induction heating from the radioactive solute metal and the pure solvent, under argon, in graphite crucibles. Pieces of these alloys were then added to the solvent to give the required solute concentration. Dendrites were grown in essentially the same manner as that described by Weinberg and Chalmer, , in which controlled orientation single crystals were grown dendritically in horizontal graphite boats, and the liquid decanted. The crystals were grown and decanted in an atmosphere of tank argon. Before decanting, a sample of the liquid was drawn up in a glass tube and allowed to solidify rapidly. The orientations of the single crystals were such that <loo> was parallel to the growth direction, and (100) in the horizontal plane for lead, and [1101 and (110) respectively for tin. With these orientations long dendrite stalks formed along the bottom of the boat in the dendrite direction (<100> for lead and [I101 for tin) from which secondary branches grew. Only these secondary branches, which grew freely in the liquid from the dendrite stalk to the liquid surface, were used in the measurements. Accordingly, effects due to substrates and oxides on the surface of the liquid need not be considered. In order to measure the solute concentration C, of the dendrites, individual dendrite stalks were cut from the decanted specimens, remelted, and formed

Jan 1, 1962

By R. H. Marshall, J. Welchner, E. S. Rowland

THIS paper presents results on an exten¬sion into the realm of high-carbon steels of some work recently published&apos; on the effects -of time at temperature, quenching temperature and prior structure on the hardenability of one 0.20 and four 0.40 per cent carbon alloy steels. It was shown at that time that unless the conditions of time, temperature and prior structure are substantially the same in performing the hardenability test as in conducting harden¬ing of parts in production, the correlation of hardenability information with the [ ] hardness and properties of production parts is often not of satisfactory accuracy. The general effects of these variables on the austenitic grain size, distribution of excess carbides and critical cooling rate have been known for many years and one or more have been investigated by Shepherd ,2 3 Davenport and Bain,4 Digges,5,6 Digges and Jordan,7 Post and associates&apos; and Roberts and Mehl,9 to mention only a few. There has been no systematic investigation, however,&apos; into the quantitative variations produced on the hardenability of commercial high¬carbon steels by changes in these factors of time, temperature and prior structure. PROCEDURE A plain carbon hypereutectoid steel, S.A.E. 52100 and Graph-Mo, a molyb¬denum-bearing high-carbon steel contain¬ing some graphite, were chosen for this investigation. The chemical analyses of these electric-furnace steels are given in Table I. [ ] The procedure used was exactly that reported previously,&apos; hence the details will not be repeated here. Normalized (1650°F.) and spheroidized prior structures were utilized on all steels with hot-rolled and quenched (1600°F. oil) prior conditions added for the plain carbon steel. The end-quench test developed by Jominy10 was selected for use in this investigation and, with the noted exceptions, the American Society for Testing Materials standard. procedure was followed. The effect of time at temperature was examined at intervals of 0, 10 and 40 min. and 4 hr., and a few i6-hr. tests were run. Salt-bath heating of the specimens was employed to control and minimize the

Jan 1, 1944

By H. I. Aaronson, H. A. Domian, A. D. Brailsford

A current study of the growth kinetics of k (hcp) plates in a Cu-Si (fcc)&apos; has generated a requirement for data 02 the chemical interdiffusion coefficient in a (termed D,) as a function of temperature at the composition of the a/a + k pJase boundary. Rhines and Mehl 2 have determined D, as a function of composition at lower silicon contents by making Matano analyses of concentration-penetration curves. However, the accelerating increase in B, which they demonstrated as the phase boundary composition is approached at constant temperature and the rapidly diminishing accuracy of this analysis as the limiting compositions of a diffusion couple are approached (the silicon-rich component of their couples contained appreciably less silicon than is permitted by the solubility limit) indicate that the required information cannot be safely obtained by extrapolation of their data. Although the quite different method employed in this study is not exact, it will be shown that the approximations made are not serious ones, particularly from the viewpoint of the prgcipal application anticipated for these data. D, was determined from the migration kinetics of the a :k boundaries formed in sandwich-type diffusion couples produced by welding a block of high-purity copper to opposite sides of a cube (* in. on edge) of homogenized high-purity Cu-5.82 wt pct Si alloy. The alloy is pure k in the temperature range employed. The surfaces of the couple components which were normal to the diffusion direction were machined accurately flat and parallel, lightly polished, and carefully cleaned. Welding was then accomplished by means of the vacuum-encapsulated pressure jig technique previously employed.3 Welding was always conducted at the intended diffusion temperature; thus the welding anneal also served as the first diffusion anneal. Subsequent diffusion anneals were performed in evacuated Vycor capsules. Following the welding anneal, one of the surfaces parallel to the diffusion direction was machined, ground, and polished flat; additional material was removed from this surface after each diffusion anneal in order to avoid any effects of composition changes. After etching,4 the average distance between a : k boundaries was measured by means of a traveling microscope with an accuracy (per measurement) of better than 1 p. Satisfactory results were obtained at four temperatures in the range 775° to 655°C; attempts to obtain data at two lower temperatures were unsuccessful, evidently as the result of the interference of surface contamination during the welding process.

Jan 1, 1969

By Richard Birk

Rf sputtered quartz has been successfully used in multilayer interconnects for MOS devices. The target potential was 2000 v peak to peak with a frequency of 13.56 Mc per sec. The sputtering rate was approximately 60A per min with an operating pressure of argon gas at 10 to 15 p. The dielectric strength is 8.0 x 10&apos; v per cm and the pinhole density is less than 2 x 10-2 per sq mm. Infrared absorption peaks for the Si-O vibrational bands we at 9.4, 12.4, and at 22.5 p. The etch rate of the sputtered SiO2 is 1200A per min. MOS devices have been fabricated using multilayer interconnects with no degradation of electrical characteristics. MULTILAYER interconnects require an insdating film between the metal layers which can be deposited below any potential eutectic temperature. Sputtered Si4, which can be deposited with substrate temperatures below 200°C, satisfactorily meets the multilayer insulation requirements and has been used to prepare MOS circuits with multilayer interconnects. The physical and electrical properties of rf sput-

Jan 1, 1969

Discussion of the paper of S. E. Bretherton, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 1481 to 1487. S. E., BRETHERTON, San Francisco, Cal.:-Since preparing my paper, our chemist, F. L. Wilson, has been experimenting with Leadville, Colo., oxidized zinc ore and Leadville zinc sulphides containing lead, operating upon 40-1b. lots at a time. His results on Leadville sulphides are as follows: The raw ore contained a trace of gold, 5.04 oz. of silver, 19.1 per cent of zinc, and 7.24 per cent of lead. After roasting the ore contained a trace of gold, 5.72 oz. of silver, 0.75 per cent of copper, 21.7 per cent of zinc, and 8.29 per cent of lead. The loss in weight by leaching was 38.8 per cent. The extraction was 42.8 per cent of the copper, 80.6 per cent of the zinc, 7.1 per cent of the lead, 0.64 per cent of the silver, and no gold. The little .silver that is extracted would be thrown down with the copper when precipitating it from the zinc and both thrown hack into the residue to be smelted. There would be no trouble in smelting the residue with nearly all the sulphur eliminated and containing less than 7 per cent. of zinc. On zinc carbonates containing silicates the results are not satisfactory. H. O. HOFMAN, Boston, Mass. (communication to the Secretary*) :¬The paper by Mr. Bretherton upon the application of ammonia and carbonic acid to the recovery of zinc as oxide from roasted sulphide ore is of interest to me, as the first installation of the Schnabel process for the extraction of zinc from a mixture of zinc oxide, lead oxide (with some cupric oxide), and pellets of enriched lead, produced in steaming liquated zinc-silver-lead crust of the Parkes process, was made at Lautenthal, Harz mountains, where I was chemist. In that capacity I carried out numerous experiments on the Schnabel process, was active in the erecting of the plant, and later had charge of it. After the Lautenthal plant had been in operation for some time a similar one was built at Hoboken-les-Anvers, but both have been abandoned, as the wet process could not compete with the distillation of the liquated zinc-silver-lead crust, now used universally in the Parkes process.

Jan 11, 1913

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By T. Yamasaki, S. Usu

Adsorption of potassium dodecyl xanthate from aqueous solutions on artificial and natural zinc sul-fides was studied by means of infrared absorption spectroscopy. The adsorption species and their stabilities varied depending upon the conditions of the surfaces of the zinc sulfides. Adsorption products were analyzed after they had been removed from the surface with pyridine. Zinc dodecyl xanthate was confirmed for surfaces covered with oxidized products while dodecyl alcohol and carbon disulfide were detected on purified or weakly oxidized surfaces. It is of great significance to study the adsorbed species of collectors on the surface of sulfide minerals with a view of increasing our understanding of the mechanism of flotation. Compared with other methods, infrared spectroscopy promises to be of particular value in determining the nature of the species adsorbed at the mineral/solution interface since it gives direct identification of the adsorption products; and, furthermore, it has an advantage over the electron diffraction technique which has been employed in similar problems in that infrared spectroscopy utilizes radiation of very low energy so that the probability of changing the unstable surface films during examination should be correspondingly decreased. Infrared spectroscopic studies concerned with sulfide mineral flotation have already been reported by several investigators on zinc sulfide-hexanthi01&apos; and lead sulfide-xanthate2,3 systems. The purpose of the present study was to investigate the adsorption of potassium dodecyl xanthate (KDX) at the zinc sulfide-aqueous solution interface by means of infrared spectroscopy. Rarely is the pure zinc sulfide-xanthate system encountered in practical flotation since zinc sulfide is usually activated with small amounts of certain metallic ions, such as copper ion. However, investigation of the pure zinc sulfide-xanthate system appeared promising for studying the fundamental mechanism of the adsorption of xanthate on the sulfide minerals. Although there are few cases where xanthates having an alkyl radical higher than hexyl are employed in practical operations, KDX was used in this study since it was reported that the adsorbability of xanthate on zinc sulfide was increased with an increasing number of carbon atoms of the alkyl radicals.4 EXPERIMENTAL Samples: Experiments were made on artificial zinc sulfide and natural sphalerite. The artificial zinc sulfide was obtained commercially from Dainihon Toryo Co. as a fluorescent pigment of the purest grade A. Considering the fact that there are often cases where the surface of sulfide minerals are apt to be oxidized so that the adsorption of xanthate at sulfide mineral/solution interfaces may be substantially affected, two different procedures were employed in preparing the samples of the artificial zinc sulfide. 1) The zinc sulfide was washed with hot concentrated ammonium chloride solution (300 g per liter) to remove surface oxidation products and followed by washing with deoxygenated hot distilled water by centrifugation until the constant electric conductivity of the solution was reached (Sample I) (specific conductivity of the solution = 8.6 x l0-5 ohm-&apos; cm-&apos;). 2) Sample I in a suspension of 5% by weight was oxidized with a 1.5% aqueous hydrogen peroxide solution for about one hour, and then was washed with distilled water as mentioned in the preparation of Sample I (Sample 11) (specific conductivity of the solution = 1.0 x 10"4 ohm-&apos; cm-&apos;). Both Samples I and II were dried under vacuum and stored in a vacuum desiccator. The specific surface areas of the samples determined by the BET method using carbon dioxide gas were 19 x l04 cm2 per g for Sample I and 35 x l04 cm2 per g for Sample 11. In addition, a sample which was derived from Sample I was also prepared. In 40 ml of 3 x 10-2 M zinc sulfate solution was placed 2 g of Sample I for 2 hours, washed with distilled water by successive centrifugation until no sulfate ion could be detected and dried under vacuum (Sample 111). The purpose of this treatment will be described later. Natural sphalerite was carefully selected by hand, ground in a mechanical agate mortar for about 40

Jan 1, 1965

A group of prominent engineers and contractors of Chicago and vicinity have cooperated in forming a Joint Committee on Military Engineering. The founders are members of all of the leading engineering and contracting organizations of Chicago, including the local branches of the national engineering societies. The purposes of the Committee are to further military preparedness among engineers, contractors and their associates by the following means: (1) Courses of lectures; (2) assigned reading; (3) studies and practical instruction in military engineering;. (4) assisting engineers to qualify as officers in the National Reserve Corps of Civilian Engineers; (5) urging enlistment in and support for engineer troops of the National Guard and such other organizations as the Government may create; (6) furthering instruction in military engineering in training camps and the attendance in them of those qualified; (7) by such other means as from time to time may be deemed advisable. The Joint Committee has already prepared a program covering the vital points outlined. To date the program is practically complete for a period extending from April 20 to July 25. Something of interest will be taken up each week, including lectures by Lieutenant-Colonel W. B. Judson, Engineer Corps, U. S. Army; two lectures by Major P. S. Bond, Engineer Corps, U. S. Army; Lieutenant-Colonel Mason M. Patrick, Engineer Corps, U. S. Army, and several exhibition drills, terrain exercises and inspection trips under the direction and guidance of various officers of the Engineer Troops of the Illinois National Guard. Additions to the program will be made from time to time.

Jan 5, 1916

By M. A. Torcaso, P. Raimondi

To study mass transport in systems simulating oil recovery processes, different porous media were saturated with a mobile (carrier phase) and a stationary phase. Slugs of carrier phase containing a small amount of solute were displaced with pure carrier phase. By analogy to the chromato-graphic processes, the velocity of the solute can be predicted from a knowledge of the partition coefficient and the saturation provided that equilibrium between the two phases exists. Equilibrium was found to exist for different porous media, solutes and rates. The conditions were varied over the range normally encountered in the laboratory and in the field. The longitudinal dispersion of a solute undergoing interphase mass transfer was also investigated. INTRODUCTION The production of hydrocarbons by gas cycling, enriched gas drive and C02 or alcohol displacement involves, among other factors, relative motion between two phases and compounds, hereafter called solute, which are soluble in both phases. The solute is carried forward by the faster flowing phase at a lower velocity than the average velocity of that phase. Retardation of the solute is caused by chromatographic absorption and desorption in the slower flowing phase and by the degree of departure from equilibrium. At equilibrium the concentration of solute in the two phases can be related by the equation* CSw = K Cso ,............(1) where C, and C are the concentration of solute in the aqueous and oleic phases respectively and K is the equilibrium ratio, or partition coefficient. Displacement theories must contain an explicit assumption with regard to equilibrium, i.e., whether the compositions can be related by Eq. 1. The existance of equilibrium depends, in general, on the relative velocity between the phases. Unfortunately, other factors such as gravity segregation and viscous fingering, also depend on velocity. For this reason, whenever effects of rate on displacement were observed,2-4 it was practically impossible to discern what caused them — lack of equilibrium or the factors mentioned above. Equilibrium between phases has been the subject of extensive studies in fields such as extraction or chroma to graphy. It has received only small attention in flow through the type of porous media encountered in oil production.5 For this reason a method was developed which makes it possible to study the movement of a solute as it is affected by rate, type of porous media, partition coefficient and carrier phase, but in the absence of segregation or fingering. The information obtained enables one to determine when the assumption of equilibrium can be made. Briefly, the method consists of (1) saturating the core with a mobile and an immobile phase, (2) injecting a slug made up of the same fluid as the mobile phase and a small concentration of mutually soluble solute, (3) measuring the lag and the peak height of the slug at arrival and (4) correlating these variables with fluid properties such as partition coefficient and mixing constants of the medium. PROPOSED MECHANISM The principles of chromatography are combined with the equation of longitudinal mixing to predict the velocity of a solute slug compared to the bulk velocity and the peak height of a slug.6-9 The equation so obtained is valid under equilibrium conditions only. Therefore, a comparison between experimental and predicted results will give a measure of departure from equilibrium. This work was done with either the oleic or the aqueous phase being immobile. For simplicity, the following development is based on the case where the oleic phase is immobile. However, the treatment is the same in either case.

Jan 1, 1966

Truman H. Aldrich &apos;78 W. S. Ayres &apos;73 Andrew A. Blair &apos;75 Walter M. Brodie &apos;72 H. M. Chance &apos;74 Fred&apos;k G Corning &apos;77 Ralph Crocker &apos;81 A. W. Crookston &apos;80 George M. Davidson &apos;81 W. B. Devereaux &apos;80 H. S. Drinker Founder William E. C. Eustis &apos;76 B. F. Fackenthal, Jr. &apos;80 John Hays Hammond &apos;81 Edward Hart &apos;81 A. Heckscher &apos;79 Henry D. Hibbard &apos;79 Francis C. Holman &apos;81 Julian Kennedy &apos;79 William,St. George Kent &apos;72 Frank Klepetko &apos;80 Wheaton B. Kunhardt &apos;80 Daniel J. Leary &apos;81 Frank Lyman &apos;77 John Markle &apos;79 Samuel Mather &apos;79

Jan 1, 1923

By Robert Keeney

IMPORTANT recent developments in the melting and annealing of non-ferrous metals include: 1. Melting of nickel silver in the vertical ring induction furnace. 2. Electric melting of stereotype metal. 3. The rotary-drum gas-fired brass melting furnace. 4. The low-frequency coreless induction furnace. 5. Finishing annealing of brass sheets with city gas1 replacing wood. -in the large brass-rolling mill. 6. Electric annealing of brass and copper tubing and sheets. 7. Replacement of oil by gas and electricity in the annealing of nickel-silver shells and stampings.

Jan 1, 1930

By G. E. Steudel

The study of the possibility of effecting a lower cost in the manufacture of pig iron reveals the importance of the ever present question of slag chemistry and volume. Factors that determine slag chemistry and volume are the impurities in the ore available, the ash-sulphur content of the coke, and a flux material necessary to promote removal of sulphur. Of these, the ores present by far the major source of impurities and what may prove to be the lowest practical slag volume with desired chemistry in one locality may be considered low or high in some other center of iron manufacture. The Chicago district is not only blessed with ores of high quality, but with excellent coke and flux materials as well. It is the intent of this paper to discuss slag problems at the South Works only, where burdens consist of Mesabi ores, Michigan stone, and coke ranging from 7 to 9 per cent ash and containing an average of 0.57 per cent sulphur. Early in the development of modern blast-furnace practice, the consideration of slags was secondary to the many adjustments of mechanical difficulties, such as furnace lines, stock distribution, stove design for obtaining higher blast temperatures, improved chemical segregation and size of raw materials. Furnace operators, after making these improvements, turned their attention to the study of other refinements in practice, of which slag chemistry appeared to be the most important. It is only within the last two decades that operators have become familiar with the various aspects of slag compositions. The industry, while rather slow in its recognition, is indebted to such investigators as Rankin,1 Wright,1 Feild,2 Royster,2 McCaffery,3 Kinney,4 Holbrook,5 and Joseph,5 whose researches concerning the elimination of sulphur within the blast furnace and the effect of slag composition upon melting point, viscosity, and desulphurizing power have established criteria for the selection of slags of the requisite quality. Large slag volumes result in higher coke consumption and cost of disposal. Any attempt to lower slag quantity must be accomplished

Jan 1, 1940

By G. E. Steudel

The study of the possibility of effecting a lower cost in the manufacture of pig iron reveals the importance of the ever present question of slag chemistry and volume. Factors that determine slag chemistry and volume are the impurities in the ore available, the ash-sulphur content of the coke, and a flux material necessary to promote removal of sulphur. Of these, the ores present by far the major source of impurities and what may prove to be the lowest practical slag volume with desired chemistry in one locality may be considered low or high in some other center of iron manufacture. The Chicago district is not only blessed with ores of high quality, but with excellent coke and flux materials as well. It is the intent of this paper to discuss slag problems at the South Works only, where burdens consist of Mesabi ores, Michigan stone, and coke ranging from 7 to 9 per cent ash and containing an average of 0.57 per cent sulphur. Early in the development of modern blast-furnace practice, the consideration of slags was secondary to the many adjustments of mechanical difficulties, such as furnace lines, stock distribution, stove design for obtaining higher blast temperatures, improved chemical segregation and size of raw materials. Furnace operators, after making these improvements, turned their attention to the study of other refinements in practice, of which slag chemistry appeared to be the most important. It is only within the last two decades that operators have become familiar with the various aspects of slag compositions. The industry, while rather slow in its recognition, is indebted to such investigators as Rankin,1 Wright,1 Feild,2 Royster,2 McCaffery,3 Kinney,4 Holbrook,5 and Joseph,5 whose researches concerning the elimination of sulphur within the blast furnace and the effect of slag composition upon melting point, viscosity, and desulphurizing power have established criteria for the selection of slags of the requisite quality. Large slag volumes result in higher coke consumption and cost of disposal. Any attempt to lower slag quantity must be accomplished

Jan 1, 1940