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By G. M. Schwartz

THERE has been considerable controversy regarding the structure and mineral constituents produced when iron ore is sintered. This investigation was undertaken in order to establish the fundamental reactions that take place in the sintering process by determining the nature of the resulting minerals. The writer's immediate interest in the subject arose mainly from the request of E. W. Davis for information based on a microscopic study of sinter submitted by him in May, 1926. In the author's preliminary work, samples of iron-ore sinter were secured from the Minnesota School of Mines Experiment Station and from commercial plants. These were polished by the usual methods for polishing opaque ores. In order to study these surfaces satisfactorily, it is necessary to magnify them rather highly, a range from 100 to 1000 dia. being used. For the higher magnifications oil-immersion lenses and an intense source of light are necessary. After the preliminary study had shown the problems involved, a series of small samples were sintered under carefully controlled conditions and with analyzed materials. Variations in the relative amounts of ore, coal and water were made in order to study the effect of each constituent. The attempt has been to arrive at a clearer understanding of the sintering process and the reactions involved without reference to any preconceived notion as to sinter. It is clear that the study of polished surfaces has yielded results not possible with thin sections alone. The thin sections made in this work were found unsatisfactory at magnification greater than 75, whereas magnifications of 1000 were easily studied with reflected light on carefully polished surfaces. A rather complete statement of observed facts is made so that the reader may form his own conclusions. The writer's interpretations are suggested.

Jan 1, 1929

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By Herty, C. H.

Iron oxide (FeO) plays an extremely important part in the manufacture of iron and steel. In the three major processes- blast-furnace, open-hearth, and Bessemer converter-iron oxide is the chemically predominant compound and controls to a large ex- tent the operation of the furnaces and the composition and quality of their respective products. In order to emphasize the importance of iron oxide in each process, they will be considered individually in some detail. THE OPEN-HEARTH FURNACE. Iron oxide is introduced into the open-hearth furnace in four ways : 1. The scrap charged into the open hearth is oxidized by the furnace gases, the amount of oxide formed depending primarily on the amount and type of scrap charged. It has been found' that with large scrap, 1.7 Ib. of FeO is formed per 100 Ib. of scrap charged, whereas with scrap of medium size about 5.3 Ib. of FeO is formed per 100 Ib. of scrap charged, when the period between the charging of the scrap and the addition of hot metal is 3 hours. 2. The decomposition of the limestone sets free CO, by the reaction

Jan 1, 1957

By J. S. Browning

The pegmatites of the Kings Mountain-Lincolnton, N. C., area constitute the largest known domestic reserve of beryl and spodumene. The reserve is estimated to contain 90 million tons of pegmatic material with 1,280,000 tons of recoverable Li2O (lithia) as spodumene.1 The pegmatites also contain 0.4 to 0.5 pct beryl disseminated throughout the orebodies. The pegmatites may contain a potential reserve of 240,000 tons beryl, equivalent to approximately 34,000 tons of BeO. Different flotation methods for separating beryl from feldspar or quartz, or both, have been developed by various investigators.2,3,4,5,6,7 On the other hand, published information is limited on concentration of spodumene-beryl ores. As the response of beryl and spodumene to flotation is essentially the same, a successful separation of the two minerals depends upon use of a selective depressant or a selective collector for one of the minerals.

Jan 7, 1961

By D. T. MacRoberts

A simple disturbance in a gas reservoir travels with a finite velocity which is nearly independent of the amplitude of the disturbance. As a result very complex transients may be set up which seriously affect observation at a well. The time of transient is much longer than commonly supposed. INTRODUCTION A change in pressure at a gas well is not propagated through the reservoir instantaneously but with a definite fin- ite velocity. Knowledge of the period ! of this transient is of value because: 1. Observations of pressure and flow-rate during the transient may affect interpretation of back-pressure tests. 2. Interference effects between wells may be used to determine continuity of formation. 3. Additional information concerning the physical characteris- tics may possibly be deduced from the behavior of a well during the transient. MATHEMATICAL DEVELOPMENT It will be assumed that the well is initially closed in and that the pressure is constant throlughout the reservoir. As the initial disturbance passes outward from the well it is further assumed that a logarithmic pressure distribution is established between the most distant point reached and the well, so that: <l> = ((/)r-<t>w) I ------------ + (/) . (1) Manuscript received at office of the Branch September 15. 1948. Paper presented at Branch Fall Meeting, Dallas. Texas. Oct. 4-6, 1948. r. = distance to any point between r and rw r = radius of drainge iw= radius of well (/) = potential (P for incompressible fluids, P2 for perfect gases) Up to the time the effect reaches the point r the production from the well will be: W= (Pr-P,,,) . (2) i b W = volume produced t = sand thickness F = fractional porosity Pr = reservoir pressure Pm = average pressure between r and rw Pb = atmospheric Pressure All pressures will subsequently be stated in atmospheres and the constant Pb will be omitted. This will be produced at a rate: dw t k (Pr³-PW2) do d 0 - . (3) log — Pw = pressure at the well k = permeability 0 = time = viscosity

Jan 1, 1949

By D. T. MacRoberts

A simple disturbance in a gas reservoir travels with a finite velocity which is nearly independent of the amplitude of the disturbance. As a result very complex transients may be set up which seriously affect observation at a well. The time of transient is much longer than commonly supposed. INTRODUCTION A change in pressure at a gas well is not propagated through the reservoir instantaneously but with a definite fin- ite velocity. Knowledge of the period ! of this transient is of value because: 1. Observations of pressure and flow-rate during the transient may affect interpretation of back-pressure tests. 2. Interference effects between wells may be used to determine continuity of formation. 3. Additional information concerning the physical characteris- tics may possibly be deduced from the behavior of a well during the transient. MATHEMATICAL DEVELOPMENT It will be assumed that the well is initially closed in and that the pressure is constant throlughout the reservoir. As the initial disturbance passes outward from the well it is further assumed that a logarithmic pressure distribution is established between the most distant point reached and the well, so that: <l> = ((/)r-<t>w) I ------------ + (/) . (1) Manuscript received at office of the Branch September 15. 1948. Paper presented at Branch Fall Meeting, Dallas. Texas. Oct. 4-6, 1948. r. = distance to any point between r and rw r = radius of drainge iw= radius of well (/) = potential (P for incompressible fluids, P2 for perfect gases) Up to the time the effect reaches the point r the production from the well will be: W= (Pr-P,,,) . (2) i b W = volume produced t = sand thickness F = fractional porosity Pr = reservoir pressure Pm = average pressure between r and rw Pb = atmospheric Pressure All pressures will subsequently be stated in atmospheres and the constant Pb will be omitted. This will be produced at a rate: dw t k (Pr³-PW2) do d 0 - . (3) log — Pw = pressure at the well k = permeability 0 = time = viscosity

Jan 1, 1949

By John V. Beall

Hard as the Revett quartzite are conditions governing the deep mines of the Coeur d&apos;Al6ne. In fourscore years of mining, heat and pressure have been the rewards of preseverance. Such obstacles are the natural concommitant to search for ore at depth. But high cost and shortage of miners is a creeping frustration of the decade. These grim observations were made on a trip to the mines of the Coeur d&apos;Al6ne in the first week of May. But the bouncy optimism of competent mining engineers and geologists overrides by far the tough conditions. This is the story of what they are doing. I think they are setting the stage for the wonder mines of tomorrow. I didn&apos;t meet all the people or see all the mines, so there are unfortunate gaps in the story. Then too, sometimes the muck and water blotched my notes, or I couldn&apos;t write fast enough or I was too tired. No matter. There is much to tell and, because it is basically a human story, I am flouting the rules of technical journalism and couching it in the neglected "I" person. First then, a little history . . . .

Jan 7, 1966

By H. K. van Poollen, H. C. Bixel

A treatment is given of the transient pressure behavior of a well located at the center of a circular region surrounded by a radial discontinuity. On either side of the discontinuity, the values of permeability, viscosity, compressibility and porosity are uniform but may be different from those on the other side of the discontinuity. The results are obtained by solving a pair of finite difference equations. The numerical solution to these equations is obtained using a digital computer. The results are compared with previously published, approximated analytical solutions to the same problem. Solutions, presented graphically, show pressure decline for constant rate fluid production. The range of variables studied include dimensionless time from &apos;0.001 to 100 and storage capacity ratio from 0.001 to 1,000. The well behaves as if it were in an infinite reservoir for dimensionless times less than 0.25. Reservoir properties near the well can be estimated in the usual manner. An overlay technique is used to match an experimental curve with one of the theoretical curves. It is possible to estimate the distance to a discontinuity by substituting the actual time t and the corresponding dimensionless time tD at which a match occurs into the equation a = (0.000264 tk1/tD , µ1 cI)I/2 where kI/ I µI cI is the diffusivity near the well, and may be estimated from data taken at early time. Several buildup curves are computed. These curves show that for early shut-in times, correct values for transmissibility are obtained from conventional analysis. However, erroneous values of static reservoir Pressure are obtained unless data at large shut-in times are taken. INTRODUCTION A mathematical treatment of the transient pressure response of a well located at the center of a region bounded by a circular discontinuity is given. Within a region (Fig. 20) the properties of both the rock and the fluid are considered to be constant on either side of the discontinuity. While these properties are considered constant, they may be different on opposite sides of the discontinuity. A discontinuity of this type could be a fluid-fluid contact or a sudden change in rock characteristics such as thickness, porosity or permeability. Analytical solutions to this problem are available. 1-3 However, they are so involved that they are of little practical use. An approximate solutionl is available but the range of times over which it is valid has not been specified. A numerical solution to a pair of finite difference equations is used to obtain the solution given in this paper. PREVIOUS WORK One of the first solutions to the problem was published by William Hurst.1 Hurst considered unsteady-state flow of fluids through two sands in series with different mobilities in each sand. He used Laplace transforms to obtain a solution for a single well located at the center of the circle enclosing the first of the two sands. In this case, the solution for the pressure change in Region I (Fig. 20) is2

By D. H. Forbes, I. B. Cadoff, H. M. Manasevit

Single-crystal silicon films have been obtained on several natural crystal faces of BeO using the thermal decomposition of silane and the hydrogen reduction of silicon tetrachloride. From an analysis of X-ray diffraction data it was determined that the following film-substrate orientation relationships exist: (111) Si 11(0001) BeO, (111) Si 11(1011) BeO, (100) Si 11f1010) BeO. and (110) Si 11(1010) BeO. An analysis of the crystallographic relationships between the film and substrate indicates that a match occurs between the silicon atoms in the film and the berylliuni ion sites in the substrate. This correspondence is in agreement with previous work on the deposition of silicon on sapphire.1-3 silicon on spinel: and tungsten on sapphire. The high resistivity, thermal conductivity, and radiation resistance of beryllium oxide make it an important substrate material for the deposition of thin films of silicon or other semiconductors. The importance of semiconductor-insulator composites to the field of integrated microelectronics has been well-documented in the case of silicon on sapphire.&apos;-&apos; The successful growth of large-area single-crystal silicon on an insulator, sapphire, was first reported in 1963.1,2 Since that time studies have been made of the crystallographic relationships between the deposited film and the sapphire substrate. On the basis of the observed relationships, a model has been proposed relative to the crystallographic requirements for epitaxy between the semiconductor film and the metal oxide substrate.3 It is proposed in this model that epitaxy is the result of a match between atoms of the deposited film and the metal ion sites of the substrate plane. This match is not limited to a 1 to 1 correspondence between sites in the two lattices. Sub- sequent studies of the deposition of silicon on spinel4 and tungsten on sapphire5 have yielded data which support this model. On the basis of this previous work it was felt that silicon on BeO should also fit this model. In the present study, the choice of substrate orientation was limited to the natural faces of synthetic BeO crystals. Of the faces available, the (0001) plane seemed the most favorable for epitaxial growth. EXPERIMENTAL PROCEDURE Silicon films were deposited from silane and silicon tetrachloride in the apparatus shown in Fig. 1. The hydrogen ambient gas was purified by passage either through a DEOXO unit, molecular sieves, and a liquid nitrogen cold trap, or through a heated Pd-Ag thimble. The gas was then mixed with the silicon source materiai and passed over the substrate which lies on a spacer above an inductively heated silicon pedestal. The following deposition conditions were used: a hydrogen flow rate of 3 liters per min with silane and silicon tetrachloride concentrations of 0.2 mole pct and a pedestal temperature of 1175" * 5°C as observed with an optical pyrometer assuming an emissivity of 1.0. Deposition was preceded by a 15- to 30-min hydrogen-etch period conducted at a temperature of 1275°C (obs). Adherent silicon films from 2 to 10 u were grown on the various BeO faces. The substrates were synthetically grown beryllium oxide single crystals ranging from 5 to 10 mm in

Jan 1, 1967

By S. Fugleberg

As a result of research work done during the planning of the Kokkola zinc plant it was found that a very efficient cementation of impurities from the suspension obtained after leaching copper and cadmium cakes was achieved by adding zinc dust to the batch without filtration after the leaching. All elements nobler than cadmium are precipitated with the exception of lead, which must be removed in a separate step. Using pure zinc dust, free from noble metals, the cadmium sponge produced will only contain elements that can be re- moved from cadmium by meltrefining. The process is thus : 1. Leaching and purification 2. Removal of lead (with BaCO3) 3. Precipitation of cadmium sponge with pure zinc dust 4. Meltrefining of briquetted sponge with NaOH for removal of Zn (and others) The paper deals with the removal of the most critical elements, i.e. Co, Ni, As, Sb, Cu, Pb, T1 in the liquid phase and Zn and T1 in the melt. A survey is also given of the behaviour of most of the other elements normally found in Cd raw material, such as Ge, Te, Se, Sn, In, Ga. It is shown that in most cases the benefit of an electrolysis in Cd production is very limited. In Kokkola 99.998% Cd is achieved by this method, but in favourable cases it may be possible to come quite close to five nines.

Jan 1, 1973

By Francis Foley

INTRODUCTION DURING the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr: Howe&apos;s laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe&apos;s death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.1 Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 2, 1926

By E. H. Rennhack, J. F. Libsch

Definite transition behavior was found in unalloyed titanium at 0.13 pct 0 equivalent. The addition of 0.5 Sn, 1.0 Al, 0.5 Al, and 1.0 Sn lowers the tvansition temperature of titanium at oxygen equivalents exceeding 0.22, 0.29, 0.40, and 0.51, respectively. Metallographic evidence indicates that progressive amounts of oxygen restrict deformation at low temperatures resulting eventually in brittle fracture. The presence of tin or aluminum is thought to alter the atomic distribution of oxygen within the titanium lattice in such a manner as to facilitate some degree of slip and twinning. 1 ITANIUM-like iron and zinc experiences a transition from ductile to brittle fracture with decreasing temperature. The presence of sufficient quantities of the interstitial elements, carbon, oxygen, and nitrogen in solid solution, has been shown to progressively lower the room-temperature impact resistance of titanium with increasing interstitial content.1"1 Ogden,et al,2 reported finding no transition from ductile to brittle fracture with decreasing temperature in iodide titanium. However, a definite transition was found to occur at 0.36 pct 0 equivalent in an alloy containing 0.47 pct carbon in solid solution. The oxygen equivalent in this case was obtained by assuming the effects of carbon, oxygen, and nitrogen in combination on the impact properties of titanium to be additive on the same basis as their separate effects on tensile strength, namely: Oe = 2/3 (pct C) + pet 0 + 2 (pet N) They concluded that the tendency toward transition behavior is dependent on the total interstitial content in solid solution and not on any one particular interstitial element. Rennhack,4 however, recently found transition behavior in iodide titanium at an oxygen equivalent of 0.17 pct. Ogden, etal3, reported that the strengthening effects of carbon, oxygen, and nitrogen in titanium decrease with the addition of tin. They showed that tin additions increase the tolerance of titanium for the interstitials, that is, 10 pct Sn permitted individual additions of up to 0.4 wt pct of the interstitial elements without any significant loss in ductility. Aluminum tends to decrease ductility and impact strength of titanium for a given interstitial ~ontent.3 Van Thyne and Kessler5 found that the solid solubility of carbon in titanium doubled in the presence of 10 pct Al. The precise effects of tin and aluminum in the nrespncp of rorvfen nn the impact properties of titanium had previously not been determined. The high oxygen tolerance of titanium containing tin may provide a suitable means for improving the impact properties of titanium containing the interstitial elements, particularly oxygen. Unlike tin, however, aluminum has a high affinity for oxygen and will reduce rutile titanium dioxide (TiO2)by a thermit-type reaction.6 Thus, the atomic distribution of oxygen in titanium might be different in the presence of aluminum. The present work was undertaken to: 1) Determine the effect of oxygen on the transition behavior of unalloyed iodide titanium. 2) Determine the effect of small amounts of tin and aluminum on the transition behavior of iodide titanium in the presence of oxygen and other interstitial~. EXPERIMENTAL Three different lots of iodide titanium were employed to prepare the alloys studied in the present work. Their chemical composition is presented in Table I. The compositions of the tin and aluminum used for alloying are shown in Table 11. Oxygen additions were made using calcined rutile titanium dioxide (TiO2)of 99.7 pct purity. Alloy Preparation—Four titanium-base alloys containing separate additions of 0.5 and 1.0 pct each

Jan 1, 1960

Discussion of the paper of DORSET A. LYON and ROBERT M. KEENEY, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin. No. 92, August, 1914, pp. 1791 to 1800. LAWRENCE ADDICKS, Chrome, N. J.-I read this paper for the first time this afternoon, and it is really worthy of a much more careful reply than I can make with such a short time to consider it, but I just want to say that I differ with Dr. Lyon in his premises and conception of what happens in a refining furnace. He cites steel as an instance where the production of special grades justifies the high cost of power in an electric furnace, and goes on to say the same will be true in the case of copper, for the reason that you will get a better quality of product. I don&apos;t think you will get a higher grade of copper,. or a better conductivity, as I will explain in a moment. The cost of fuel in the Eastern plants is somewhere between 30c. and 40c. per ton of copper refined, and, if my memory serves me correctly, in an open-hearth steel furnace it is something like $1.25, so it is evident that steel could be handled to better advantage than copper on the basis of fuel. Now, taking the Great Falls plant to compare with is not quite fair, because that plant operates under peculiar conditions. The furnaces are relatively small; the coal is very bad and is very high in sulphur. No one would think of using a coal with 3.6 per cent. sulphur were anything better available. Due to these conditions, the amount of slag is inordinate, it being quoted as 3.5 per cent., and it is necessary to use lime, as there is a tendency to have troubles from arsenic owing to the very high current density used. I think he has taken about as hard a case as he could pick out. Now as to the conductivity of copper, my own idea about the reason that melted copper does not give as high a conductivity as pieces drawn directly from a cathode, or native copper, is that in the latter case the impurities are present as a mechanical mixture, while after melting they are chemically combined with the copper, which is a very different condition. Further, it is necessary to take the sample from a relatively smooth and consequently pure part of the cathode, as otherwise it would not draw. The same with the mass of copper; you pick out a good solid part of the copper, which is not representative. In fact, the refiners have all found they could not take fair samples of cathodes for a chemical analysis. It is always customary to use wire-bar copper -for the purpose of sampling, and the impurities are several times as great as shown by samples taken from .the cathodes. I think if we examine all of the examples he has given of cases where copper is higher in conductivity, it will fit with that explanation. For example, the Elmore process is a direct electrolytic deposit. Incidentally, at the present time there are a number of ex-

Jan 12, 1914

By O. N. Carlson, S. A. Bradford

Discontinuous yielding in tensile tests was observed in V-O alloys in the temperature ranges of 150° to 175°C and also 350° to 400°C. The magnitude and intensity of the serrations were found to vary considerably with oxygen content. Maxima were observed in tensile and yield strengths and in the strain-hardening coefficient at the higher temperature only. The strain rate sensitivity was observed to be negative between 150° and 400°C. THIS investigation was undertaken to study the effect of oxygen on the tensile properties of iodide vanadium in the temperature range of 25o to 450°C. Brown1 observed an increase in strength between room temperature and 400°C in vanadium metal, and found that oxygen and nitrogen had a rather pronounced effect on the strength and ductility. A maximum in the tensile strength was observed by Rostoker et al.2 near 300oC and by Pugh3 around 450°C for calcium-reduced vanadium. Pugh also found a maximum in the yield strength and in the strain-hardening exponent, and minima in the elongation and strain rate sensitivity at the same temperature. Eustice and Carlson4 reported the appearance of serrations in the stress-strain curves between 140° and 180°C in iodide vanadium containing 600 ppm O. These anomalies in the mechanical properties indicate that strain aging occurs in vanadium, but the impurity or impurities responsible for the above-mentioned effects have not been identified. The phenomenon of strain aging is usually characterized by the return of the yield point after interruption of a strength test. In the temperature range where strain aging occurs, the yield and tensile strengths attain maximum values, elongation and strain rate sensitivity exhibit minima, and discontinuous yielding is generally observed in the stress-strain curve. Cottrell5, 6 has postulated that strain aging is due to the migration of solute atoms to dislocation sites to produce locking after the dislocations have broken free from their impurity atmospheres during the initial yielding. At the strain-aging temperature the process is a dynamic one in which the solute impurity atoms diffuse to the vicinity of the moving disloca- tion producing "locking" which gives rise to maxima in the tensile strength and serrations in the elongation curves. Cottrel17 has noted that discontinuous yielding in iron occurs when the diffusion coefficient of nitrogen, D, and the strain rate, i, are related by D = 10-9 €. EXPERTMENTAL PROCEDURE The vanadium metal employed in this study was prepared by the iodide refining process as described by Carlson and owen.8 A representative analysis of the vanadium used in this investigation was: 150 ppm O, <5 ppm N, <1 ppm H, 150 ppm C, 150 ppm Fe, 70 ppm Cr, <50 ppm Si, 30ppm Cu, 20 ppm Ni, <20 ppm Ca, <20 ppm Mg and <20 ppm Ti. Alloys containing from 200 to 1800 ppm O, all of which lie in the solid solution range of the V-O system, were prepared by arc melting vanadium together with portions of a high-oxygen master alloy. The master alloy was prepared by tamping pure V2O5 into holes drilled in a vanadium ingot and arc melting this five or six times in an inert gas atmosphere, inverting the button between each melting step. The oxygen content of the master alloy was then determined by vacuum fusion analysis. Vanadium containing less than 150 ppm O was prepared in the following manner. A bar of iodide vanadium was deoxidized by sealing it in a tantalum crucible with a few grams of high-purity calcium. This was held at 1100°C for 4 days to allow time for the oxygen to diffuse to the surface and to react with the calcium vapors. The calcium oxide product was later dissolved from the surface of the bar with dilute acetic acid. In this way vanadium containing from 20 to 50 ppm O was prepared. Sample Preparation. The are-melted ingots were cold swaged into 3/16-in. diam rods and these were machined into cylindrical tensile specimens with a reduced section of 1.00-in. length and 0.120-in. diam. The test specimens were annealed for 4 hr at 900°C in a dynamic vacuum of mm of Hg to remove hydrogen from the metal. This recrystal-lization treatment produced a uniformly fine-grained structure with a mean grain size of approximately 0.06-mm diam. The oxygen contents reported in this paper were determined by a vacuum fusion analysis of the tensile specimens after testing. Analyses for other interstitial or metallic impurities showed no significant changes from that of the original material. Tension Tests. Tension tests were performed on a screw-driven tensile machine at a constant cross-head speed of 0.01 in. per min. Tests at elevated temperatures were carried out by heating the

Jan 1, 1962

By W. J. Babyak

The habit planes for hydride precipitation in large grains of alpha zirconium and Zircaloy-4 were determined in specimens containing 161 and 136 ppm hydrogen, respectively. In zirconium, the hydride platelets precipitated on various pyramidal planes inclined to the basal plane at angles ranging from 10 to 50 deg and 75 to 90 deg. Hydrides were most frequent at inclinations of about 20 deg and 90 deg. In Zircaloy-4, hydride plates were inclined to the basal plane at angles vanging from 5 to 25 deg with the predominant inclinatioiz equal to 12 deg; no platelets were found near the prism plane position. In both zircoinium and Zir-caloy-4, hydrides were principally, but not exclusively, parallel to (1011) type planes. When the Zircaloy-4 gmins were subjected to tension stresses of 12,100 psi and 19,400 psi during hydride precipitation, the hydride habit was unchanged except that precipitation favored those habit planes which were inore nearly perpendicular to the stress direction. The stress-orientatioiz effect increased with the magnitude of the stress. THE hydride habit plane in a zirconium has been determined by several investigators. Langeron and Lehr1 in 1956 found platelets parallel to (1010) slip planes. In 1962, Westlake and Fisher2 confirmed these findings and showed that hydride precipitation on twin planes, as reported by Kunz and Bibb,3 was probably due to incomplete removal of worked metal from specimen surfaces. Secondary habit planes, ( 1011) and (1015), were also found by Westlake and Fisher under particular charging conditions where a hydride layer may have existed at the hydrogenation temperature. Most recently, walters4 and westlake5 again observed the (1010) habit exclusively in zirconium. Louthan and hgermans have reported that hydrides precipitate on various ( 101l ) and (112l) planes positioned 31.5 to 90 deg to the basal plane in Zircaloy-2. The present investigation was concerned with the hydride habit in Zircaloy-4 in relation to that in zirconium and the possible change in habit when precipitation occurs under stress. The latter consideration was prompted by the stress-orientation phenomenon originally reported by Marshall and Louthan.7, 8 I) EXPERIMENTAL Materials and Specimens. Chemical analyses of all materials are given in Table I. The zirconium specimen was a 1 by 4 in. section cut from wrought crystal bar that was hot-rolled at 790°C to 0.300 in. and cold-rolled to a final thickness of 0.095 in. All surfaces were mechanically polished and then chemically polished with a solution of H2O, HNO3, and HF (10:10:l by volume) prior to annealing. Grains as long as 0.25 in. were grown by thermally cycling the specimen three times (in 10-5 mm Hg vacuum) between 825" and 1000°C at approximately 125°C per hr. The specimen was isothermally annealed at 825°C for 24, 40, and 120 hr after each cy-

Jan 1, 1968

By G. S. Brooks

The tendency of the oxides of such metals as aluminum, zinc, chromium, and calcium to form compounds at high tempera tures with iron oxide is well established by past investigation. Data of this reaction, as developed in laboratory research, have been contributed by Burleigh, Hofman, and Wells, in America, and by many others abroad. A partial bibliography of the subject is appended. From these authorities we learn that the ferric oxide here has the function of an acid, giving in the case of ZnO a zinc ferrite, with a normal composition of ZnOFe2O3 This formation of zinc ferrite particularly affects the success of such processes as leaching or magnetic separation, and thus becomes practically important to the metallurgist. But the meager existing data do not entirely agree; and quantitative results from muffle-practice are conspicuously absent. Furthermore, it being of some general importance to the zinc smelter in both roasting and reduction, the following few notes of operations oil a commercial scale are contributed: I. Physical Properties of Zinc Ferrite. As formed for the most part synthetically by investigators, zinc ferrite exhibits characteristic physical properties, such as octahedral crystals, dark color, and a density over 5, together with a slight magnetic attractability. In examining with the microscope many products of mechanical muffle-roasting kilns, it is, however, impossible to find individual grains which can be identified as consisting entirely of zinc ferrite. The variety of colors, especially where each grain of blende was mechanically free from marcasite, rather conveys the impression of a partial ferritization of the grain. One side or end, for example, may often have the hard, dense surface and dark red to black color of the ferrite, while the balance shows the usual light yellowish brown of a normal iron-free blende.

Jan 1, 1914

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry&apos;s law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry&apos;s law is obeyed, one canthen use the Van&apos;t Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors&apos; Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott&apos;s results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By R. F. Mehl, B. Lustman

THE formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.1 It is necessary here only to enumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type-i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [I] where X is the thickness of the alloy layer, k the reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such. a plot has been con¬sidered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.3 In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varies with temperature according to the Arrhenius equation k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative, thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase .4 The reaction layers tend to have a

Jan 1, 1942

By Sam F. Carter

FOR some time melters and metallurgists have recognized the fact that steels may be made to identical compositions as ordinarily analyzed, but with considerable variations in physical properties. Good melting practice signifies a combination of furnace operations that will produce steel with consistently good physical properties after proper consideration of cost, production efficiency, and chemical control. In acid practice, these operations may be classified fundamentally as: (I) the oxidizing boil, (2) recarburization and deoxidation, (3) slag adjustment, and (4) final deoxidation. These operations affect the properties of the steel through variations in the minute quantities of several microscopic, submicroscopic, and dissolved constituents, which are out of reach of ordinary analyses but are very influential upon the crystallographic slippage and the molecular cohesion of the structure. One of these constituents is the FeO left in solution in the steel. Herty has shown that steels high in dissolved FeO have decreased ductility and impact and increased hardness and electrical resistance. There is also much evidence that FeO in solution affects carbon solubility and diffusion, and consequently abnormality and carburizing behavior.

Jan 1, 1947

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970