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By J. A. Cordier

USINOR has conducted four blast furnace tests with formcoke made from marginal coals in the pilot plant of HBNPC ("H. B. N." process) in four different blast furnaces of various sizes and with medium and high grade burdens. The tests in which up to 30% of the blast furnace fuel burden was replaced by HBN formcoke yielded good results on furnaces ranging in hearth diameters from 5.6 to 9.5 m. The tests demonstrated that: - the slight increase of pressure drop in the stack did not prevent smooth operation at record production rates with the same blowers - the total coke rate was not significantly affected, but there was a slight increase of the calorific value of the top gas - the hot properties of the formcoke are satisfactory as seen from the samples withdrawn at the tuyeres and tapholes. At the end of the two months test on BE nº 2 of Dunkerque, the hearth was as permeable and clean as with good standard coke. Our conclusion is that HBNPC formcoke made from lean coals is an adequate substitute for conventional coke in the range of 20 to 40% replacement, which is of interest to USINOR.

Jan 1, 1977

By O. S. True, C. H. Herty

It is well known that manganese will desulfurize molten iron through the formation of manganese sulfide, which, being only slightly soluble in the metal, rises to and enters the slag where it remains as such (mixer slag) or is converted partly or wholly to calcium sulfide (basic open-hearth slag). The reaction by which manganese sulfide is formed is Mn + FeS = MnS + Fe. This reaction is generally considered to be reversible, although McCancel states that such is not the case. The experimental work was carried out to confirm the results of Roh12 as to the reversibility of the reaction. Six trials are herein considered. In each 200 gm. of electrolytic iron free from manganese and sulfur were melted in a pure zirconia crucible in a carbon resistance electric furnace. To the melted iron in runs 2, 3 and 4 metallic manganese and manganese sulfide were added to give 1, 2 and 4 per cent. manganese respectively, with 0.50 per cent, of sulfur in each. In runs 5, 6 and 7, metallic manganese and iron sulfide to give the same proportions of. manganese and sulphur as in runs 2, 3 and 4, were added. The melts were held molten in the furnace for an hour and then cast into small ingots. The results of these melts are as follows: Ingredients of Charge Analysis or InRot ManOaneBe, SulfUR, ManOaneBe. SULFUR, Run Material Charged PeR Cent. PeR Cent. Per Cent. PeR Cent. 2 MnS + Mn............... 1.0 0.452 0.636 0.367 3 MnS + Mn............... 2.0 0.50 1.57 0.310 4 MnS + Mn............... 4.0 0.50 2.81 0.230 5 FeS + Mn................ 1.0 0.50 0.647 0.397 6 FeS + Mn................ 2.0 0.50 1.45 0.374 7 FeS + Mn................ 4.0 0.50 2.73 0.195

Jan 1, 1925

By J. A. Snyder, W. L. Finlay

G. Edmunds—Solid solubility is considered to be of either the interstitial or the substitutional type. Is it possible, in a binary alloy as the simplest case, that some of the solute atoms are present in the normal lattice sites (substitutionally or filling lattice vacancies) while simultaneously others are in interstitial positionss One might even ask whether a distribution of the two types may be the normal situation. H. M. Meyer—Metastable states of interstitial atoms occupying vacant lattice sites possibly occur as well as of substitutional atoms squeezed in between regular matrix positions. However (as we know since Hume-Rothery), the solute atoms choose between the two kinds of solutions; consequently, every solute will be unequivocally either substitutional or interstitial in the equilibrium state of the solid solution. M. Balicki—In view of the fact that the authors apparently correlate the analysis of the alloys at the ingot stage with the properties exhibited at the testing stage, I would like to ask whether this is a fully justifiable procedure. In other words, how good are their determinations of solute concentration for correlating them with the mechanical properties. The answer to this question may explain some of the divergencies. Assuming good enough homogenization of the samples and exact determination of mechanical properties the position of the plotted experimental points will depend solely upon the accuracy of composition determination. If this is not accurate, say due to loss or pickup of elements during processing from the ingot to the testing stage, or due to a systematic error in the method employed for obtaining solute concentration data, the points will deviate from their true position and may align themselves along a different curve than the one expected. H. V. Kinsey—We have been studying the creep-rupture properties of titanium-base alloys at 1000°F. In the course of this work, anomalies in behavior of the alloys that would suggest that the material under test was becoming stronger as the test progressed have been observed. If this was so, the most likely explanation that we could think of was that the test bars were absorbing oxygen and nitrogen from the air during the test and were thereby becoming strengthened. In an attempt to determine the strengthening effect of absorbed oxygen and nitrogen the following experiment was conducted. A length of cold-rolled titanium was supplied by the E. I. du Pont Co. Two test bars, having a 1/4 in. diam gauge length, were prepared from this material. One bar was tested in the as-received condition. The second bar was heated in air at 1550°F for 100 hr and subsequently air cooled prior to testing. A testing temperature of 1000°F was employed. The results of these tests are tabulated in table 11. In the author's opinion, is it reasonable to assume that the bar that was exposed to air at 1550°F for 100 hr was stronger because it absorbed oxygen and nitrogen from the air during this heat treatment? W. L. Finlay (authors' reply)—Direct experimental evidence for or against Mr. Edmunds' interesting suggestion will probably never be available. It seems possible, however, that mixed interstitial-substitutional solid solution might well occur with interstitial elements. The less likely possibility of interstitial solution of a normally substitutional element like copper in aluminum was recently discussed at length by the

Jan 1, 1951

By L. C. Uren, E. J. Bradshaw

This paper presents the results of a group effort by a number of University of California students and faculty members, and the authors attach their names primarily in the capacity of editors and interpreters of the data thus assembled. In addition to the writers, the following individuals have made substantial contributions in time and effort in the conduct of this research: Dr. A. J. Carlson, Associate Professor of Petroleum Engineering; J. E. Gosline, University Research Assistant; C. F. Bedford, G. W. Mikulasek and H. S. Conder, senior and graduate petroleum engineering students; H. Bachman, G. Spencer and G. W. Gard, mechanicians in the Department of Mining and Metallurgy. Acknowledgment is also due the Research Board of the University, the Department of Mining and Metallurgy, and Prof. F. H. Probert, Dean of the College of Mining, for continued cooperation in securing mechanical assistance and funds for the purchase and assembly of apparatus. Significance of the Pressure Gradient The expulsion of petroleum from its reservoir sand doubtless is due to expanding natural gas intimately associated with the oil, to the hydrostatic pressure of encroaching edge waters, and to gravitational influences. These forces may operate independently or collectively. In any case they subject the fluids stored within the reservoir sands to elevated pressures, thus causing movement of oil and gas through the productive formations toward the lower pressure of the well outlets. This movement is opposed by pore friction, capillarity and adhesion: resisting influences brought to bear by the reservoir sand on the moving fluids. The magnitude of the resisting force is influenced directly by the viscosity, surface tension and density of the oil, as well as by the properties of the gas. The more rapid the rate of flow, the greater will be the resistance offered, and the greater will be the energy consumed.

Jan 1, 1932

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 A. J. Jacobs, G. Katz

MANY of the studies of intermetallic compounds containing uranium were performed during the early 1940's under the aegis of the Manhattan Project. Subsequently, much of this work was declassified and published after 1949. In some instances this early work, completed with relatively impure materials, represents the only source of X-ray diffraction powder data available in the literature. In the case of the intermetallic compound U,Fe some discrepancies in the powder pattern exist in the literature. Since this compound has been prepared in this laboratory, it is believed that the publication of the indexed powder pattern would help clarify the conflict in the literature. In studies of the U-Fe system, Gordon and Kauf-mannl and Grogan and Clews2 independently reported the intermetallic compound U,Fe in 1950. The crystal structure was described by Baenziger, Rundle, Snow, and Wilson3 in 1950. It is isostructural with U,Mn, U,Ni, and U,Co and crystallizes in a body-centered tetragonal lattice. The lattice constants determined by Baenziger et al. are: giving an X-ray density = 17.7 g cm-3 for 4 mol per unit cell. The compound used in this study was prepared by melting a stoichiometric mixture of the constituent metals in an argon-arc furnace using a nonconsum-mable tungsten electrode. Before the argon of 99.98 pct purity was introduced into the furnace, it was passed through CaC1, to remove water vapor and afterwards through a stainless steel tube containing calcium turnings heated at 600°C for the removal of nitrogen and oxygen. The purity of the uranium used was better than 99.9 pct and that of the iron was 99.97 pct. Before and during melting a zirconium getter was used to further purify the argon atmos-

Jan 1, 1962

By Peter Soo

Pvestrained Ferrovac E iron has been neutron-irradiated at approximately 90°C to an integrated flux of 1020 nut (E > 0.82 mev]. The irradiation was found to produce an incveased temperature dependence of the flow stress in addition to a greatly increased athemal stress. Measurements of the flow stress and stress relaxation, from which the activation volume and activation energy for slip were deduced, show that neutron irradiation changes the rate -controlling slip process to one based on dislocation interactions with tetragonal distortions which are Produced around submicroscopic interstitial loops in the lattice. The study indicates that without prestraining prior to irradiation the chances of detecting a change in the rate -controlling slip process are greatly reduced because in the initial stages of slip a substantial fraction of the radiation defects are swept out of the slip plane by gliding dislocations. Thus, activation parameters which are subsequently measured are representative of a greatly reduced defect density and would not differ appreciably from those for unirradi-ated material. The large increase in the athermal component of the flow stress is probably connected with the presence of depleted zones in the lattice which are introduced by irradiation. ALTHOUGH fast neutron-irradiation has not been observed to markedly alter the activation parameters for slip in bcc metals,' small but significant changes do occur. Most experimenters agree that irradiation predominantly increases the athermal component of the yield stress.'-= In addition to this, Laidler and smidt7 have shown that in iron irradiated to 5 X 10" nvt and molybdenum irradiated to 10" nvt, changes occur in the activation volumes for slip. A similar conclusion has been reached by Milasin and Malkin8 for irradiated iron. Work by Ohr et a1.5 shows that for Ferrovac E iron, irradiated to 1.2 X 1016 nvt, small increases in the activation energy for slip also occur. So far these changes in the activation parameters have not been explained on a firm theoretical basis. One important factor which would minimize the chances of detecting a change in the slip mechanism upon irradiation is the presence of "channeling" which has been observed in molybdenum,9 niobium,10 and iron.11These channels are formed by gliding dislocations which sweep irradiation defects out of the active slip planes and thereby create zones in which continued dislocation motion is encouraged. The activation parameters for the dislocations gliding in the defect-free channels would, therefore, be similar to those for unirradiated iron and a change in the rate-controlling slip process would be difficult to detect. In the present work, an attempt has been made to reduce the effect of uneven deformation on the measured activation parameters for slip in neutron-irradiated Ferrovac E iron polycrystals, so that a more realistic assessment of the effects of neutron-irradiation could be made. Primarily, the experiments involve the irradiation of specimens which had been prestrained to 9 pct elongation at room temperature prior to insertion into the reactor. It was hoped that the introduction of a large number of evenly distributed dislocations would substantially decrease any channeling effect which might otherwise occur. MATERIAL AND EXPERIMENTAL PROCEDURE The starting material was vacuum-melted Ferrovac E iron, an analysis of which is given in Table I. The standard tensile specimen had a gage length of 1.125 in., a cross-sectional diameter of 0.120 in., and a re-crystallized grain size of 1.2 x 10-3 in. All tensile tests were conducted on a floor model "Instron" tensile machine at a strain rate of 3 x 10-4 per sec. The irradiation of the prestrained specimens was performed in the Brookhaven High Flux Beam Reactor to an integrated flux of 1020 nvt (E > 0.82 mev) at a temperature of about 90°C. All specimens were excap-sulated in high-purity aluminum sheaths which were lightly swaged around the samples to ensure good thermal contact. Subsequent measurements on the irradiated specimens showed that within experimental accuracy the swaging had not deformed them. EXPERIMENTAL RESULTS Fig. 1 shows the flow stresses for a series of unirradiated control samples. In order to produce a comparable dislocation substructure throughout the test sm range, all specimens were prestrained

Jan 1, 1970

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957

By K. A. Jackson, G. A. Chadwick, A. Klugert

The diffusion field ahead of a lamellar interfnce is analyzed using an electrical analog. A self-consistent solution is obtained for the shape of the interfnce and the diffusion field by an iterative process. The solutions presented here are for a 50-50 eutectoid or eutectic, The shape of the interface is found to he independent of growth velocity and lamellar spacing, and to depend on the relative values of interfacial free energies at the phase houndaries . The mode of growth of lamellar eutectics and eutectoids has been a subject of much interest for many years.1-4 Mehl and Hagel 1 have shown photomicrographs taken by Tardif when he attempted to determine experimentally the shape of an advancing pearlite interface; the results are completely ambiguous. Brandt' and schei13 have made approximate calculations of the composition ahead of a lamellar growth front. The shape of the advancing front and the composition distribution ahead of the front are difficult to calculate because one depends on the other. It is the purpose of the present paper to describe a method by which this calculation has been done. Lamellar-eutectic growth usually occurs under conditions where the growth is fairly rapid, and the interface temperature is close to the eutectic temperature. The growth rate is usually determined by heat flow. Eutectoid growth, on the other hand, can best be studied by quenching to some temperature, and allowing growth to proceed isother-mally. In both cases the growth is believed to be controlled by diffusion* rather than by the atomic kinetics of the transformation. This being the case, a single treatment of the diffusion equation will apply to both cases, provided the region of the interface in a eutectic may be considered to be isothermal. If a part of the interface could appreciably change its thermodynamic driving force by advancing ahead of or lagging behind the mean interface, then the two cases would not be similar. Eutectics normally grow in temperature gradients of the or-der of a few degrees per centimeter. The normal eutectic spacing is the order of a few microns. Part of the interface would have to extend many lamellar spacings ahead of the mean interface before it experienced sensibly different conditions. The interface temperature is usually a few tenths of a degree below the eutectic temperature so that temperature differences of the order of one-thousandths of a degree (a displacement of one lamellar spacing) would be unimportant. Protrusions large compared to the mean spacing do occur when one phase only grows into a eutectic liquid. This is usually a dendritic type of growth, and easily distinguishable from the lamellar mode of growth. A single treatment of lamellar growth will apply equally well to both eutectic and eutectoid decomposition. At the interface, which as shown above is essentially isothermal, the difference between the equilibrium eutectic temperature Teu and the actual interface temperature Ti, can be divided into two parts: 1) the composition varies across the interface, so that the local equilibrium temperature is not Teu; and 2) the interface is curved, so that the local equilibrium temperature is depressed according to the Gibbs-Thompson relationship. This undercooling can be written as Teu-Ti =?T = mAC(x) + a/r(x) [1] where ?C(X) is the departure of the composition at a point x on the interface from the eutectic composition, see Fig. 1, r(x) is the local radius of curvature at a point x on the interface, m is the slope of the liquidus line on the phase diagram, and a is a constant given by where s is the interfacial free energy, TE is the equilibrium temperature, and L is the latent heat of fusion. The calculations in this paper will be made only for the case where the phase diagram is symmetric, that is, the eutectic occurs at 50 pct, the liquidi have the same magnitude slope m at the eutectic temperature, and C,, the amount of B rejected when unit volume of a freezes, see Fig. 2(a), is the same for both phases. As shown in Fig. 2(b), the composition ahead of the a phase will be rich in B, the composition ahead of the ß phase will be rich in A. The composition at the phase boundary is the eutectic composition. The difference between the local liquidus temperature and the actual tempera-

Jan 1, 1964

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By W. Barbarowicz, H. E. Uhland

AT the Noralyn mine and mill of International Minerals & Chemical Corp. in Bartow, Fla., process instrumentation has been incorporated in three departments-mining, flotation, and preparation. Use of the dragline is the most difficult aspect of the mining operation to control automatically. At the Noralyn mine there are two draglines, a Bucyrus-Erie 1250-B with 29-yd bucket and 235-ft boom and a Bucyrus-Erie 1150-B with 21-yd bucket and 215-ft boom. These are equipped with a minimum number of instruments, but further instrumentation would increase the operator's efficiency.

Jan 7, 1957

By C. Pin, J. Bruce Wagner

In order to demonstrate the role of defect chemistry in the solid state to a process-metallurgy reaction, laboratory experiments were carried aut to remove copper from liquid lead using lead sulfide which had been doped to provide definite concentrations of cation vacancies. The removal of copper decreases in the order: bismuth- or antimony-doped PbS, undoped PbS or tin-doped PbS, and silver-doped PbS. The data are explained using the simple mass -action law and in terms of the exceedingly rapid interstitial diffusion of coppw in PbS to vacant cation sites. Results are in agree-ment with thermodynamic predictions and certain industrial practices that copper may be removed from lead below the limit of its coexistence with pure Cu,S and pure PbS. The role of defects in solids has been exploited in semiconductors and many device applications, in explaining tarnish formation, dissolution rates, and mechanical properties. The application of these principles to many process-metallurgical problems has not received as much attention. It was the purpose of this study to illustrate the role of defect structures of solids in a process-metallurgical application. When lead is refined, the ore, galena (PbS), is reduced by a series of operations to liquid lead (lead bullion) containing impurities such as copper, bismuth, antimony, arsenic, and silver depending on the original composition, the fluxes added, and the particular type of operation, see Fig. 1. In order to produce a pure lead, a series of refining operations are carried out. A typical lead-bullion analysis before drossing is shown in Table I. Copper is removed first as its presence increases the zinc consumption during the desilverizing process. For preliminary copper removal the lead bullion is brought to a temperature of 440°C in a kettle of 60 metric tons capacity. Some tar (or sawdust or resins) is usually added and the kettle is cooled slowly to 400°C while the liquid is stirred. A solid phase, called a dross, floats on top of the liquid and the particles of the solid phase adhere to the tar. This "hot dross" is collected. It contains mostly lead and copper which are partly oxidized and/or sulfurized if the lead bullion contains some sulfur.*

Jan 1, 1963

By Billy L. Crowder, John M. Fairfield

The implantation of B+ , P+, and As&apos; into silicon has been studied with the purpose of making shallow p-n junctions. The influence of such parameters as 1) ion energy, 2) target orientation and temperature, 3) total dose, and 4) annealing schedule was investigated. An energy range of 70 to 300 kev was used for boron and phosphorus implants and up to 500 kev for arsenic. It is found that the experimental projected range agrees well with theory and that shallow junction depths can be made reproducibly. ION implantation has received much attention recently as a technique for doping semiconductors. Specifically, it has the potential of supplementing or replacing the diffusion process as a method for making p-n junctions. In a few specific cases it has been used successfully to make semiconductor junction devices. Potential advantages of ion implantation doping over diffusion techniques are: 1) It affords greater control of shallow junction depths (< 0.2 µ) while maintaining high peak concentrations. This is particularly important for high-speed switching devices, since lower junction capacitances and resistances can be achieved. 2) More precise registration of small planar structures can be realized if proper masking procedures are employed. This advantage is especially useful in the design of high-density integrated circuits. It has been used to advantage in FET fabrication since the edge of the source or drain can be aligned precisely at the edge of the gate electrode.&apos; 3) Ion implanatation permits lower temperatures than diffusion techniques. This factor alleviates the problem of compatibility of diffusivities often encountered when designing multiple-junction structures. Also, the lower temperatures create fewer thermal defects and dislocations, which may account for the high efficiency of some ion-implanted solar cells.2 4) Impurity profiles can be more easily tailored to resemble ideal distributions. Successful exploitation of the potential advantages of ion implantation techniques will depend on increased knowledge and understanding of the subject. The factors likely to be influential in determining impurity distribution profiles in ion-implanted single-crystal targets have been reviewed by J. F. Gibbons.3 In addition to the mass and energy of the implanted ion, the total dose, target orientation, and target temperature are important parameters. The annealing temperature required for removing lattice damage and incorporating the implanted species on an electrically active site is very important. This paper describes an investigation of some of these factors. Implants of boron, phosphorus, and arsenic into silicon have been studied. Energy ranges of 50 to 300 kev were used for boron and phosphorus and up to 500 kev for arsenic. In addition to the implantation energy, the effects of total dose, target temperature, and post implant anneal have been investigated. EXPERIMENTAL PROCEDURE The implantation targets were silicon wafers cut from Czochralski-grown crystals, lapped, and chemically polished. The orientations were (111), (110). and (100) with misorientations of up to 7 deg from the principal axis. For this study, accurate target alignment (i.e., within 0.1 deg) was not available and quoted misorientation values should be regarded as approximate . The implantation equipment consisted of an ion source, a 300-kev linear accelerator tube, an electromagnetic separator, and the associated target supporting and beam focusing assemblies. The ion source was a simple oscillating electron type source,4 which has been described elsewhere.5 The gaseous compounds BF3, PF5, and AsH3 were used as ion sources for B+, P+, As+, and AS+&apos;. Analyzed current levels of up to 20 pamp could be obtained; however, for this investigation target current levels of 1-3 µ amp were usually employed. The analyzed ion beam was collimated through a double slit (1.4 x 0.4 cm) and swept perpendicularly to the long axis of the slit such that an area of about 2 sq cm on each target was covered. Dosages of around 1015 cm-2 were normally employed, but smaller amounts were also used for comparison. A uniform flux density over the bombarded area was assured by the continuous use of profile monitors similar to those described by Wegner and Feigenbaum.6 Post-implant annealing was accomplished in an argon atmosphere in a temperature range of 600" to 950°C. It was not part of the purpose of this investigation to study the annealing kinetics; however, some isochronal and isothermal anneal experiments were conducted to determine the time and temperature necessary to render a reasonably high portion of the implanted ions electrically active (i.e., higher than 50 pct). Post-implant anneal temperatures of around 900° and 600°C were required for boron, and arsenic and phosphorus implants, respectively. Arsenic and phosphorus implants increased in conductivity rather abruptly at the proper anneal temperature of the isochronal curve, but boron increased more gradually over a wider range. Isothermal anneal curves were reasonably flat after 10 min, so an anneal time of 1/2 hr was used for the experimental results described below. The profiling techniques were: 1) neutron activation analysis, 2) differential sheet resistance,7 and 3) junction staining.8 The differential sheet resistance technique is commonly employed in this type of study. Its principal disadvantage is the uncertainty of the ef-

Jan 1, 1970

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By David T. Day

In the summer of 1898, a demand suddenly arose for commercial quantities of the element osmium. At least half a ton was wanted for the manufacture of a new incandescent light. This led the writer to examine localities where platinum had been reported, in order to determine whether osmiridium mas contained in the crude platinum. With the co-operation of the concern most interested, the Welsbach Light Company, and in company with its President, Col. William E. Barrows, I visited most of the leading American localities where platinum has been obtained. I also wrote to every available placer-mine in the West for samples of the heaviest sands, in order to test them for platinum. The results of this inquiry are given in the present paper. Distribution. The notices of the occurrence of platinum in this country given in scientific journals include two interesting observa tions in the East. One concerns a nugget described by Peter Collier of Washington, D. C.,* and said to have been found on land adjacent to the village of Plattsburgh, N. Y., which weighed 104.4 grammes, and contained sufficient chromite to reduce the specific gravity from 17.35 for the heaviest portion to

Jan 1, 1901

1. Any society of undergraduates at a technical school, comprising students in any branch of engineering, metallurgy, chemistry, geology, etc., may be recognized by the Board of Directors in its discretion as an Affiliated Student Society, and its name, together with the names of its President and its Secretary, may be published in the Bulletin or the Year Book of the Institute. The individual members of such a society will not be catalogued as individual members or associates of the Institute, but may at any time be proposed for election as members or associates of the Institute, in the usual way. 2. Membership in an Affiliated Student Society, certified by the official representative thereof, and accompanied with suitable testimony as to character and qualifications, will have special, weight with the Membership Committee of the Institute, in its consideration of the proposal of a candidate for membership or for Junior membership.

Jan 1, 1923

1. Any society of undergraduates at a technical school, comprising students in any branch of engineering, metallurgy, chemistry, geology, etc., may be recognized by the Board of Directors in its discretion as an Affiliated Student Society, and its name, together with the names of its President and its Secretary, may be published in the MINING AND METALLURGY of the Directory of the Institute. The members of such a society will not be named individually on the membership list of the Institute, but may at any time be proposed for election as associates or junior associates of the Institute, in the usual way. 2. Membership in an Affiliated Student Society, certified by the official representative thereof, and accompanied with suitable testimony as to character and qualifications, will have special, weight with the Membership Committee of the Institute, in its consideration of the proposal of a candidate for membership or for Junior membership.

Jan 1, 1923

1. Any society of undergraduates at a technical school, comprising students in any branch of engineering, metallurgy, chemistry, geology, etc., may be recognized by the Board of Directors in its discretion as an Affiliated Student Society, and its name, together with the names of its President and its Secretary, may be published in the MINING AND METALLURGY of the Directory of the Institute. The members of such a society will not be named individually on the membership list of the Institute, but may at any time be proposed for election as associates or junior associates of the Institute, in the usual way. 2. Membership in an Affiliated Student Society, certified by the official representative thereof, and accompanied with suitable testimony as to character and qualifications, will have special, weight with the Membership Committee of the Institute, in its consideration of the proposal of a candidate for membership or for Junior membership.

Jan 1, 1923

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.&apos; Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.&apos; The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953