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By H. H. Stout

IN the early fall of 1925, the writer was conducting, in the Ledoux and Co. labora-tory, New York, experiments directed to-ward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point, The apparatus consisted of a vertical 1-in. dia. silica tube about 12 in. long, heated on the outside, The cathodes were broken to pass a8-in. mesh, and a current of various differ-ent gases was passed up through a 4-in, long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to i500° to 1600°F. and the gas treatments lasted from 3 to 6 hr, The writer observed that whenever reducing gas (H2 or CO) was used, these cathode par-ticles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc, had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500°F," Smoot's reaction, after a few moments considera-tion, was, "It looks perfectly all right to me."

Jan 1, 1940

By Magnus Troilius

The method of using the bromine process of determining sulphur in steel, described below, is in successful use at the Midvale Steel Works. Ten grams of drillings are weighed out and put into the 1/2-liter flask A, with long neck. The flask is connected with a wide glass tube C', which, in its turn, is connected with the absorption bulbs B, containing HCI, 1.12 specific gravity, and ahout 5 C.C. of bromine. The wide tnbe C causes the vapor to condense and flow back into the flask A during boiling. The bulbs B connect with a long glass tnbe, which may be made to carry off the bromine fumes through a hole in a window, or, better still, through a flue with powerful draught. The connections being made, 100 C.C. of boiling water are run in through the thistle tube T. The air is thus completely driven out of the flask. 100 C.C. of HC1 (about 1.19 specific gravity) are then run in. When the gas begins to run rattler slowly through B, heat is applied until boiling gradually ensues. The steel being completely dissolved, the apparatus is disconnected, and the contents of B rinsed out into a beaker of 100 C.C. capacity, into which a few C.C. of a concentrated solution of BaCI, have been previously introduced. Heat is then applied (best by means of the hot iron plate) until the bromine is completely driven off and the BaSO, has settled nicely to the bottom. The BaSO4, is then filtered off on a small

Jan 1, 1884

By A. J. Sedriks

ALTHOUGH the occurrence of a readily visible tarnish on the stress-corrosion fracture surfaces of titanium alloys tested in oxygenated nitrogen tetrox-ide solutions has been reported,' the possibility that the formation of this tarnish is a requirement for cracking to proceed does not appear to have been considered. It has been proposed that failure occurs in this system as a result of some electrochemical-mechanical process.2 However, recent studies3-6 of the stress-corrosion cracking of a brass in certain ammoniacal solutions, which also cause visible tarnishing, have led to the view that failure occurs by the repeated formation and fracture of a brittle surface film of cuprous oxide. The purpose of this note is to point out the similarities which exist between the tarnish which forms on a brass and that found on titanium alloys failed in nitrogen tetroxide, and to suggest, by analogy, that a similar tarnish-rupture mechanism may be operative in the latter case. The titanium alloy selected for the present study contained 5.2 pct Al, 2.5 pct Sn, 0.025 pct C, 0.16 pct Fe, 0.014 pct N, 0.012 pct H, 0.07 pct 0, and 0.002 pct Mn by weight. Vacuum-annealed alloy strips measuring 4 by 0.25 by 0.04 in. were used to prepare self-stressed test specimens. Each specimen was made from two strips by bending the end portions and spot welding them together to produce curved sections of uniform bending stress. (The exact details of preparing such specimens have been described by Lisagor el al.7) The curvature in the strips determines the ma-magnitude of the outer fiber stress, which in the present specimens was 100,000 psi (yield stress = 120,000 psi). The specimen surface in the spot-welded end regions was shot-peened to induce compressive stresses and thereby eliminate the possibility of stress-corrosion cracking in these regions. The test environment was nitrogen tetroxide, initially containing 99.5 pct N2O4, 0.1 pct H2O, and 0.08 pct C1, through which oxygen had been bubbled for 30 min. During testing the tetroxide was subject to an oxygen pressure of 250 psi. The duration of the test was 96 hr, and during this time stress-corrosion cracks propagated through some 50 pct of the thickness of the specimens. After testing, the tarnish was liberated from the fracture surface by immersion in a methanol-5 pct bromine solution, and then examined by electron dif- fraction and transmission electron microscopy using a JEM-7 electron microscope. The possibility that the bromine solution had affected the structure of the tarnish was investigated by an "in silu" examination of the stress-corrosion fracture surface using a reflection electron diffraction attachment designed for handling bulk specimens. Typical areas of the tarnish liberated by the me-thanol-bromine solution are shown in Fig. 1. Fig. l(a) reveals that the tarnish consists of individual platelets, and from Fig. l(b) it can be seen that the platelets are joined together to form a semicontinuous film, the boundaries of the titanium substrate grains being retained in the tarnish. Electron-diffraction patterns taken from these areas exhibited diffraction spots typical of a monocrystal. The diffraction pattern shown in Fig. 2 was taken from the central area in Fig. l(n). Monocrystal patterns obtained from areas containing numerous individual platelets can only be explained by assuming that their growth is governed by the titanium substrate (i.e., their growth is epitaxial). In other areas, the tarnish had folded over or became mechanically damaged, and these areas gave diffraction patterns consisting of "spotted" rings, enabling interplanar spacings of the tarnish lattice to be determined. These spacings, measured using a

Jan 1, 1968

By J. E. Flinn, E. R. Gilbert

Recently, Green reported some high-temperature, 0.60 to 0.89 T3, creep results on unalloyed tantalum. From his study he determined an activation energy of 114 kcal per mole for steady-state creep using the T, differential-temperature method25 for testing. He accounted for the difference between this value and 110 kcal per mole for self-diffusion by the temperature dependence of the elastic modulus, 4 kcal per mole. This reported activation energy is in apparent disagreement with that which can be determined from Green's isothermal data, which we have plotted as log creep rate vs 1/T in Fig. 15. From this figure, it appears that there are two activation energies of -185 kcal per mole at the higher temperatures and -75 kcal per mole at the lower temperatures. It is not obvious that the data can be fitted to a straight line corresponding to an activation energy of 114 kcal per mole. One is led to two possible conclusions regarding Green's study: there are two discrete processes controlling the creep rate from 0.60 to 0.89 Tm or the apparent activation energy is not discrete but continuously increases with increasing temperature. The former speculation would be in closer agreement with the high-temperature creep behavior of tungsten.28 The apparent disagreement between the activation energies determined by the AT and isothermal methods certainly suggests that further study on the high-temperature creep of tantalum is needed.

Jan 1, 1967

By J. F. Enrietto

It is shown that one cannot approximate the broad internal friction Peaks observed in the Fe-Mn-N system as the sum of a number of subsidiary Peaks and still vetain the concept of a single relaxation time. Furthermore, the approximation of manganese affectirg only nearest neighbor interstitial sites is shown to be incompatible with the experimental results. The results of this experiment show that the influence of manganese in the ferrite lattice extends over 3 to 4 atomic distances. NUMEROUS experiments have shown that the presence of relatively small amounts of substitutional alloying elements can profoundly affect the profile of the damping spectrum in the vicinity of the Snoek peak in bee metals.1-7 Dijkstra and Sladekl observed this phenomenon in Fe-Mn-N alloys where it appeared as a broadening and shifting of the Snoek peak to higher temperatures. The authors interpreted this as being the result of a superposition of two damping maxima—the normal Snoek peak, located at its usual position and having a normal half-width, and an interaction peak having a normal half-width, but occurring at a somewhat higher temperature. They prclposed that the interaction peak was caused by nitrogen atoms jumping from Fe-Mn sites to Fe-Fe sites, the Fe-Mn interstitial sites having one manganese and one iron atom as nearest neighbors, and the Fe-Fe sites having two iron atoms as nearest neighbors. They further suggested that the Fe-Mn sites had a lower energy than the normal Fe-Fe sites because of the presence of the adjacent manganese atoms. From the relative heights of the two postulated damping peaks, the dif-

Jan 1, 1962

By W. L. Penberthy, H. J. Ramey

Experimental work on the combustion oil recovery process has consisted of both laboratory and field studies. Although field experiments are the ultimate test of any oil recovery process, they are costly, time consuming and difficult to analyze quantitatively. Laboratory combustion tube experiments can be opertzted far more rapidly and cheaply, but are subject to scaling and interpretation problems. This paper points out some important design problems, operational criteria and considerations in2portunt to interpretation of results. An analytical hcut model of movement of a burning front axiully along a cylinder with heat loss through an annular insulation was developed. The result was used to identify steady-state temperatrrre distributions both ahead of and behind the burning front, with and without heat loss. Results indicate potential operating limitations on the minimum burning front rielocity (or air flux) which may be used for any given combustion tube. Results also enable estimating the effective thermal diffusivity and over-all heat loss from experimental data and thickness of the brnning zone. Resu lts of operation of a combustion tube constructed recently verify this preliminary theory in the region immediately ahead of and behind the burning front surprisinRly well. INTRODUCTION Many field and laboratory studies of the forward combustion oil recovery process have been conducted since the early publications of Kuhn and Kochl and Grant and Szasz2 in 1953 and 1954. In view of the complex and costly nature of this type of investigation, it is not surprising that no complete theory of the nature of the forward combustion Drocess is yet available. However, gross effects are understood well enough that reasonable design procedures are available for planning field operations. Nelson and McNeil 3,4 have published two comprehensive papers concerning design procedures. One major consideration in planning field operations is the fuel concentration at the burning front. Fuel concentration controls air requirements — an important cost factor in forward combustion. Although fuel concentration can be estimated from field test results by various methods, results are subject to great uncertainty in view of natural limitations on experimental observations. Nelson and hlcNeil4 recommend that fuel concentration be determined from laboratory combustion tube studies. Fuel concentration is only one of many important factors which can be studied by combustion tube experimentation. An obvious goal of imporrance must be development of a comprehensive theory of the forward combustion process. If a theory of this process can be established which matches controlled laboratory experimentation, it should be possible to apply this theory to field operating conditions with some confidence. Laboratory combustion tube studies have already yielded important information concerning the combustion process. However, details concerning the design, construction and operation of combustion tubes are rare. Combustion tubes used by various investigators vary in size, length and mode of operation. Therefore, one purpose of this paper is to present considerations important to design, construction and operation of a combustion tube. In regard to previous combustion tube studies, attention is called to Refs. 1 through 9. These references describe a wide variety of equipment types and present a great deal of pertinent experimental data. In general, combustion tubes usually consist of thin-walled stainless steel tubes containing an oil sand pack mounted within a pressure jacket. Provisions have often been made to heat the tube ex tern a lly by separately controlled heaters to reduce heat losses. This step usually permits operation at low air fluxes (air rate per square foot burning front surface) similar to those encountered in field operations. Burning is usually conducted from the air inlet end of the tube to the outflow end. The tube orientation used has been vertical or horizontal. For vertical tubes, burning has been conducted vertically downwards. As a result of laboratory studies, many of the

Jan 1, 1967

By R. M. Rose, K. A. Jones

Resistive measurements ulere made on superconducting niobium single crystals in transverse magnetic fields. Crystals were grouln in both high and ulfrahigh vacua, doped with stnall quantities of oxygen, and annealed in ultrahigh vacua at temperatures from 900' to 1350°C. Maxima in the fluxoid pinr~ir~g force were observedfor the [100] and [210] directions. The increase of the critical current density with dissoved oxygen was seen to saturate at relatively low concentration. This behavior, and the variation of J, and residual resistivity (as a function of oxygen content and annealing) of both clean and dirty gassy) crystals, is seen as a consequence of the formation of clusters with (210)~b habit planes and (200)ffo common boundaries. These suboxide clusters are apparenlly stable at high temperatures and very low oxygen concentrations. It is generally known that dissolved oxygen at concentrations well below the solubility limit sharply increases the critical current density of superconducting niobium.' Such a result would not be expected if Nb-0 solutions were random, not even as the result of segregation on the scale usually encountered in solid solutions. According to the Kim-Anderson theory of flux creep,' the critical transport current density is determined by the pinning force Fp associated with some feature of the microstructure. As the Lorentz force. a or (J X R), of the transport current in the magnetic field approaches Fp, flux creep and then flux flow occur. The pinning force is expected to be quite small if the heterogeneity involved is significantly smaller than tte range of coherency which for niobium is circa 250~.~ Although the strain field of an individual oxygen atom in the niobium lattice is relatively large, it does not seem plausible that individual atoms could be so effective as to account for the data. Also, ~ramer~ found that straining and strain aging specimens containing small amounts of oxygen on occasion decreased the residual resistivity. A possible explanation for the above behavior may be found in the work of van Ooijen and van der Goot,= who found that annealing changed J, for niobium foils containing oxygen, and they attributed the changes to ordering of the oxygen atoms. This phenomenon has been observed by other investigators using X-ray and PROCEDURE Cylindrical 4-in.-diam niobium single crystals with axial orientations [ill], [110], [112], and [oo~] were grown from pure niobium, see Table I for analysis, in an ion-pumped ultrahigh-vacuum system using the electron beam floating zone technique. Total pressure during growth was lo-'9 torr: the oxygen partial pressure was less than lo-" torr, as determined by a mass spectrometer. These crystals will be referred to as the "clean" crystals. Similar crystals were also grown in another system at a pressure of 5 X 10"6 torr. These crystals will be referred to as the "dirty" crystals. Specimens 14 in. long were cut from the as-grown crystals and one end was polished down to no. 600 carbide paper smoothness. A back-reflection Laue photograph was then taken in order to fix the crystallo-graphic directions transverse to the crystal. The critical current density J,, the current density necessary to produce a voltage drop of 1.0 pv between voltage leads placed a in. apart, was determined as a function of the magnitude and direction of the transverse magnetic field and of the oxygen concentration. The technique and experimental arrangement was essentially similar to that of Tedmon et al.' In the remainder of this paper, the azjmuthal angle $ for the field H is referenced to the [ I101 direction in all four crystals, and oxygen was added in small equal increments by anodization and annealing.7 The resistivity ratio, RR, of the resistance at room ternperature to that at 4.2"K (H =7.00 kG) was determined as well.

Jan 1, 1970

By H. Margolin, A. Coucoulas

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKcll radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuAl2, and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band.1,4 Europium in EuAl2 appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref. 1. One of the other phases was identified as Co5Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acia Cryst., 1959, vol. 12, p. '162. A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently hiher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1 week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By Francis M. Rich

BEFORE the world-wide depression, the primary purpose of most blast-furnace operators was to produce a maximum tonnage of pig iron per day for each furnace in blast. Some attention was paid to the conservation of labor and raw materials, but the idea was well established that low-cost pig iron was attainable only when each furnace was producing a high tonnage. After the depression had set in, the picture changed considerably. Each blast-furnace operator was forced to run his plant in a manner that best fitted the economical set-up of his company. A great deal of thought was expended on the different methods of operation, always with the idea of making each product in a way that would best serve his company financially. Because of this abnormal condition, the blast-furnace man was compelled to indulge in various practices of which many had been believed to be next to impossible up to that time. The ultimate purpose of these innovations was either one or a combination of the following: 1. To produce only enough pig iron for immediate consumption at a minimum cost. 2. To produce gas for boiler or mill use to supplant some higher priced fuel. 3: To consume the coke produced at the coke plant, which was often viewed as a byproduct. 4. To protect the cash position of the company. These conditions were met by diverse methods, some of which were: 1. Slow or decreased wind. In some instances the blast blown was held as low as 25 per cent of the normal volume. 2. Intermittent operation, in which the furnaces were shut down or "fanned" at frequent intervals.

Jan 1, 1935

By V. R. Garflas, J. W. Ristori, R. V. Whetshel

Preliminary estimates indicate that world consumption of petroleum products and related fuels in 1937 shattered previous records with a figure of 1,920,000,000 bbl.; that is, 124,000,000 bbl. more than the 1936 total. The writers, as in previous years, have been unable to account for all the available supply in 1937. This "unaccounted-for" supply, which formerly was thought to go largely into storage in foreign countries, was close to 53,000,000 bbl. in 1933; 93,000,000 in 1934; 111,000,000 in 1935; 75,000,000 in 1936 and 148,000,000 in 1937. As this discrepancy between supply and demand continued year after year, it became evident that other reasons than additional foreign stocks were responsible for it. It can now be stated that the "unaccounted-for" supply (see Table 1) goes to take care of: (1) consumption of petroleum products and related fuels for military purposes, the figures of which have been and are kept confidential by foreign countries, (2) additions to stocks to be consumed for military and nonmilitary purposes in foreign countries on which likewise no information is available, (3) errors incurred in the conversion of figures of production of crude oil, its products and related fuels from "weight" units, as used in Russia, for instance, to their American or "volume" equivalents and vice versa, and (4) to the lack of reliable statistics on production and consumption, particularly from Russia, the

Jan 1, 1938

By S. E. Haszko

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuA12 and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band. 1,4 Europium in EuAl2, appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref 1. One of the other phases was identified as Co,Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acla Cryst., 1959, vol. 12, p. '162. The Influence of Hydrogen on the Lattice Parameters of Ti-Sn Alloys A. Coucoulas and H. Margolin A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently higher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By B. Ancker, E. R. Parker

The small-angle dislocation-boundary density of nickel and some of its alloys was investigated as a function of strength. It was found that the strength is a linear function of the density for pure nickel and for Ni-Ti alloys, but not for Ni-Co alloys. The results are interpreted in terms of dislocation theory. THE processes by which metals deform are still poorly understood, even though there has been a concentrated research effort in this field during the past fifteen years. Single crystals and individual grains in polycrystalline aggregates often develop a subgrain structure when deformed. Substructure formation occurs as a result of local plastic bending and its development is augmented by annealing at moderate temperatures.' Investigations made to date, largely qualitative in nature, have shown that the substructure is composed of a network of small-angle boundaries. The purpose of the present paper is to present some quantitative data on substructure (obtained by X-ray techniques) and to correlate the results with the strength of the metal in which the substructure existed. Nickel and some of its alloys were used for the experiments. The presence of certain kinds of foreign atoms greatly alters the formation and effect of the substructure. Polycrystalline tensile specimens were prepared from high purity nickel, two Ni-Ti alloys, and two Ni-Co alloys; the composition of these materials is given in Table I. Tensile specimens having a reduced section 1/4 in. diam by 3 in. long were machined from materials which were refined, cast, forged, and swaged in the authors' laboratories. The specimens were annealed for 1/2 hr at 1150°C, a treatment which produced grains having a diameter of approximately 0.5 mm. This rather large grain size was used to facilitate later examination of the substructure. Duplicate specimens of pure nickel and of each alloy were strained various controlled amounts in tension at room temperature and recovered for 1 hr at 800°C. (This strain induced prior to recovery will be referred to hereafter as the "prestrain.") One of each of the recovered specimens was pulled in tension at room temperature to obtain the stress-strain curves. The other bar was cross-sectioned in the gage length, carefully polished, and deeply etched to remove all cold-worked material. This specimen was then examined by the X-ray microscopic technique2 to determine the nature and magnitude of the substructure. The use of duplicate specimens permitted a direct correlation between tensile properties and substructure characteristics. X-ray microscopic studies were made with an apparatus constructed to have an average resolving power of about 4 microns. The monochromatic radiation reflected from grains which were oriented favorably was recorded on fine-grain photographic plates. These were examined at Xl00 which represents the true magnification, since there was essentially none in the X-ray system. This permitted detection of angular differences between subgrains of as little as 10 min. A very large number (over 100) of grains for each specimen was examined at this magnification and the number of substructure boundaries per grain was tabulated. An accurate relative measure was obtained under fixed experimental conditions, e.g., same grain size, resolving power, magnification, etc. The greatest source of error lay in counting the subboundaries, but this proved to be surprisingly small when repeated counts were made by different investigators. Furthermore, as the subsequent analysis indicates, whatever human error was introduced was not significant. Analysis of the Substructure Data When the number of substructure boundaries per grain was plotted against the frequency, skew (asymmetrical) distribution curves of the type shown in Fig. 1 were obtained. These are smoothed curves for the 1 atomic pct Ti in nickel alloy subjected to various prestrains and are representative of the curves obtained with all the metals. Since skew-distribution curves cannot be analyzed by elementary statistical methods, detailed investigations were undertaken in order to 1—test the consistency

Jan 1, 1955

By R. Kerby, T. R. lngraham

The rates of cadmiuln cementation from buffered solutions were studied on both the cylindrical and circular faces of a rotating zinc disk. The activation energies are equivalent on both surfaces, but the rate is more rapid on the cylindrical face. At higher temperatures and at pH values above 6.4, the rate of deposition increases because of an increase in the cathodic area of the deposit. The rate may also be increased by decreasing the thickness of the diffusion layer by rapid stirring. The presence of small amounts of copper, cadmium, lead, iron, or aluminum in the zinc does not affect the cementation rate, but when srnall amounts of copper, cobalt, and arsenic were present in the solution cadmium deposition ceased shortly after it started. Small amounts of copper in solution become cemented with the cadmium to form a coarse deposit of Cd3Cu. When zinc ores containing cadmium are processed for electrolysis, the cadmium appears with the zinc in the leach liquors. Because of the discharge potential of the cadmium ion and the hydrogen overvoltage on metallic cadmium, the cadmium ion must be removed prior to zinc electrolysis to prevent its codeposition. Cadmium is usually removed from acidic zinc sulfate solutions by cementation on zinc. When zinc sheets are used with the appropriate conditions of pH and temperature, a finely divided, high-purity cadmium powder is obtained; it floats to the surface with attached hydrogen bubbles and, after careful washing, may be processed directly to a marketable product.' The reaction on zinc sheets is relatively slow because of the limited amount of exposed cathodic area on the sheets. A much more rapid reaction is obtained when zinc powders are stirred into the solution, but this procedure does have a potential disadvantage: some unreacted zinc may be trapped in the cemented cadmium and thus lower its grade.1 The equilibrium constant at 25°C for the displacement of cadmium by zinc is of the order of lo", which indicates that at equilibrium the displacement would be essentially quantitative and no back reaction need be considered. This indication is not entirely true, however, because in the presence of oxygen any loose cadmium which is out of contact with metallic zinc tends to redissolve after cementation.' The overall effect is much the same as that to be expected if the equilibrium constant were much smaller. Previous experimental work on cementation reac- tions3 is in general agreement that the rates of cementation usually follow first-order kinetics. The metal on which cementation occurs is considered to consist of anodic areas from which metal dissolves and cathodic areas onto which the reactive metal is cemented. For the reaction to continue, the cemented deposit must remain open and porous for the removal of ions. Usually, the deposited metal influences the rate of cementation; when it blocks the pores in the deposit, the rate of cementation will be decreased. Alternatively, when the cemented metal grows as den-drites or as coarse powder the cathodic area is correspondingly increased and the rate of cementation increases,3 Thus, it is only during the initial stages of cementation, prior to the development of deposit effects, that the kinetic behavior of the reaction may be studied without ambiguity. In this paper, experiments will be described for cementation of cadmium from dilute solutions onto the surface of a rapidly spinning zinc cylinder. The effects of ionic concentration, disk rotation speed, temperature, and impurities will be described. APPARATUS AND PROCEDURE The apparatus used for the experiments was described in a previous paper.4 It consisted of a 2-liter vessel in which the contents were protected, against oxidation, by a stream of prepurified nitrogen. The vessel was immersed in a water bath which controlled

Jan 1, 1970

By Y. C. Liu

IN the study of the rolling recrystallization of face-centered-cubic metals, a most unusual observation is the frequent occurrence of a sharp re-crystallization texture of cube orientation. Although the general conditions under which this texture occurs are known,2,3 its origin is still not well understood. Based on the observed relationship between the {110}<112> deformation texture and the (113}<211> recrystallization texture, regardless of the effect of alloying elements2,4,5 or the symmetry of the deformation texture,&apos; there is a strong indication that a specific component of the deformation texture is related to a specific component of the recrystallization texture. Using the rotational reorien-tation relationship as a means of correlating the deformation and recrystallization textures, it was proposed that the deformation component which related the cube texture has {358)<523> indices."&apos; The investigation reported here was undertaken to seek experimental evidence for the validity of this proposition. Experimental Procedure Two copper single crystals having an initial orientation within 2" of (358) [523] indices were prepared in the manner described in Ref. 5. The purity of the copper was between 99.94 and 99.97 pct. The original dimensions of the crystals were as follows: specimen A, 0.465 in. thickness, 0.844 in. width, and 0.955 in. length; specimen B, 0.535 in. thickness, 1.120 in. width, and 1.36 in. length: Rolling was done on a laboratory rolling mill according to the following schedule: 0.010 in. per pass to 50 pct reduction in thickness, 0.005 in. per pass to 70 pct reduction inthickness, 0.002 in. per pass to 85 pct reduction in

Jan 1, 1958

By Strathmore R. B. Cooke, Thomas E. Ban

MUCH experimental work has been performed on the mechanism of agglomeration and pelletizing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiöld and Ilmoni1 much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the microstructures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was. added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.2 Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl methacrylate monomer.3 The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45°C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer&apos;s method.4 Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wüstite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1952

By R. J. Jackson, D. E. Williams, W. L. Larsen

The phase diagram of the Ta-Zr system is presented with a discussion of the methods used in its determination. The solidus contains a minimum at 1820°C near 25 wt pet Ta. A complete solid solution exists at elevated temperatures between tantalum and ß zirconium. This solid solution decomposes monotectoidally at 800°C and 12 wt pet Ta. The maximum solubility of tantalum in a zirconium is slightly less than 2 wt pet, and decreases with decreasing temperature. The solubility of zirconium in tantalum is 5 wt pet at the monotectoid temperature and about 2 wt pet at room temperature. THIS investigation was part of a program of research on refractory metal alloy systems having potential application in nuclear reactor technology. Preliminary prop-ess has been reported in the Ames Laboratory annual research reports.l Most of the previously reported work on the Ta-Zr alloy system consisted of partial phase diagram investigations and the determination of the mechanical properties of the zirconium-rich alloys. Anderson eta1.2 studied alloys containing up to 30 wt pet Ta as part of an investigation of several zirconium alloy systems. These investigators also determined some of the mechanical properties of the alloys at room temperature and 650°C. In a discussion of Anderson&apos;s work, Pfei13 suggested that the bright phase in the microstructures of the intermediate alloys is a tantalum-rich solid solution or an intermediate phase in a matrix of ß zirconium solid solution. Litton,4 Keeler,5 and Chubb6 determined the mechanical properties of zirconium-rich alloys at ambient and elevated temperatures. Van Thyne and McPherson7 reported the tensile properties

Jan 1, 1962

By S. Wiederhorn

The energy and force of interaction between a crack and a slip band have been calculated. When the distance between the crack and the slip band is greater than the dislocation spacing of- the slip band, the force on the cgrack is perpendicular to the slip band. The energy needed to propagate a crack against this force can be lawe enough to pevmit crack propagation parallel to noncleavage planes. SEVERAL recent experiments have demonstrated the occurrence of crack-slip band interaction in ionic crystals having a NaC1-type structure. Stokes, Johnston, and Lil have studied the nucleation and growth of cracks in MgO. From their observations, they conclude that slip bands have the ability to halt and stabilize cleavage crack nuclei. Gilman2 has shown that a crack, propagating along a (100) cleavage plane in a previously deformed LiF crystal, tends, at certain points within the crystal, to switch to (110) planes. He reasons that plastic deformation reduces the cohesive energy of the (110) planes below that of the (1130) planes, making possible (110) crack propagation. Keh3 has demonstrated that when indentations are made in MgO, crkcks form along (110) planes at the indentations. Gilman2 attributes the formation of these cracks to plastic cieformation. There is some doubt as to the formation of cracks on (110) planes. Kuznetsov4 in his discussion of crack propagation in rock salt, shows that splitting along (110) planes requires 1.76 times as much energy as splitting along a stepped (100) surface. Therefore, the observed (110) cracking in LiF and

Jan 1, 1962

By J. E. Fox Jr., J. L. Lummus, J. P. Gallus

Fresh water or brine drilling fluids may be kept free of suspended drilled solids by the addition of a water soluble acrylamide-carboxylic acid copolymer at the flowline. Addition of from .01 to 0.2 lblbbl of the polymer solution to drilling fluids containing less than 5 per cent clay solids by weight causes the solids to flocculate and settle rapidly to the bottom of the pits. Solutions of the polymer injected at the pump suction reduce the loss of water to permeable formations without impairing the permeability to oil. The use of drill-itlg fluids clarified with the polymer has resulted in increased drilling rates, extended bit life, and lower drilling fluid costs. INTRODUCTION Field experience and the results of a number of investigations have established that the accumulation of solids in drilling fluid reduces drilling rate.&apos;-&apos; Drilling with water makes possible higher drilling rates than can be achieved with mud but in many areas drilling with water may not be feasible because of the possibility of encountering high formation pressures or by-dratable formations. To combat these conditions, the drilling fluid must possess certain physical properties such as viscosity, density, fluid loss, etc., which require the presence of solids. The current trend in drilling fluid treatment is to maintain as low a percentage of solids as is possible without harmfully affecting the mud properties needed for drilling. Mechanical separating devices such as wet cyclones and decanting-type centrifuges are proving to be an economical means of controlling the percentage of solids and thereby maintaining low solids muds. Also: special muds have been developed for the purpose of retarding the hydration of drilled solids so that they may be more easily removed by shale shakers or settling pits. In some areas, such as West Texas, the characteristics of some formations will permit drilling with water. However, because of the dispersion of drilled solids, it is usually not possible to maintain clear water even with the aid of mechanical separators, or by utilizing large settling pits. For this reason the commonly used term "water drilling" is a misnomer since the water usually contains some solids. Because of the improved drilling rates and other benefits which might be effected, a laboratory and field study was made of the use of flocculating agents for maintaining clear water for drilling. PROCEDURE Laboratory—Solids Settling Two techniques were employed to determine the effectiveness of flocculating agents in settling solids from drilling mud. First, the rate of fall of solids was measured in graduated beakers containing mud treated with various flocculating agents. Natural gum, oil-in-water emulsions prepared with ethoxylated nonyl phenols and diesel oil. and a powdered synthetic acrylamide-carboxylic acid copolymer* (hereinafter referred to as "polymer") were tested as flocculating agents in both fresh water and salt saturated muds containing 4 per cent solids. The polymer was not added in the powder form directly to the muds but was first dissolved in water in a concentration of 3.5 lb/bbl. The polymer solution was then added directly to the mud. The concentration of the flocculating agents, including the polymer, was varied. High rates of fall of the solids indicated high flocculating efficiency. A second technique consisted of measuring the time in minutes required to obtain clear water at the pump suction after addition of the various flocculating agents at the flowline. These tests were made using a model mud circulating system having a total volume of approximately 10 gal. The natural fresh water and brine muds used contained 4 per cent solids. A sketch of the circulating system appears in Fig. 1. The circulating rate

By Gordon H. Geiger, John M. Svoboda

One mechanism of metal penetration into mold aggregates by cast steels is vapor state mass transport. In order to further understand and quantify this mechanism, the steady-state diffusion of metallic vapors was studied at 1250" to 1600°C in controlled oxygen pressure atmospheres by measuring the weight loss from a metal bath whose vapors were allowed to diffuse through a porous aggregate compact held at constant temperature. Mass transport rates substantially greater than those predicted from the assumption that the vaporizing species was the elemental metal vapor were observed. Vaporization rates were found to increase with an increase in the oxygen partial pressure in the gas atmosphere with maximum vaporization occurring at oxygen partial pressures just below those in equilibrium with a liquid oxide layer at the given temperature. When the liquid oxide layer was present, no vaporization was observed. Metal carbonyls were ruled out as the vapor species involved because of their thermodynamic properties. The species with the enhanced volatility were deduced to be gaseous metal-oxygen molecules, probably the polynuclear oxides (FeO)2 and (Mn0)2. Diffusion followed the ordinary diffusion mode, and Knudsen diffusion is not important in normal foundry molds. The interdiffusivities of the metallic vapors and the mold atmosphere, through the porous aggregates, were measured. The effective interdif-fusivity of the vapor species and mold atmosphere through the aggregate may be expressed as follows: Deff,12 - — where E is the void fraction of the aggregate and 7 is the "tortuosity factor". Aggregate material had no effect on diffusion rates, and the only relevant parameter was the void fraction. Values for 7 ranged from 3 to 6 for normal foundry aggregates with 4 being considered a good representative value. An area of interest in high-temperature metallurgical processes which has received little attention in the past is the diffusion of metal vapor species in porous aggregates. Research into the metal penetration phenomenon&apos; in foundry molds has shown that a major penetration mechanism is the vapor transport of metallic species into the porous foundry sand molds, followed by condensation of metallic films on the sand grains. Considerable study of the vaporization of metallic species has been reported in the literature, and the vapor transport properties of many metallic species have been determined.2&apos;3 Many instances have been observed where the vaporization behavior could only be explained by the existence of a metallic species with a vapor pressure greater than the elemental metallic species. These species were identified or, in some cases, presumed to be carbonyls,4,5 hydroxides,6-9 or vaporous oxides.10-16 The diffusion of gases through porous aggregates has received considerable attention in the literature pertaining to catalysis, although primarily at low temperature, and more recently in the literature concerned with ore reduction.17-22 The following experiments were devised and carried out in order to determine the nature of the metallic species involved in the metal penetration phenomenon, and the effective diffusivities involved. EXPERIMENTAL APPROACH Steady-state diffusion was selected for experimental convenience. The experimental systems used, shown in Figs. 1 and 2, consisted of a porous aggregate specimen contained in an impermeable alumina tube held above, and just separate from a metal bath. The entire system was held at constant temperature and pressure in a furnace with a controlled oxygen partial pressure atmosphere. After a brief period of nonsteady state behavior, a steady flux of metal vapor through the porous aggregate will develop due to the concentration gradient of metallic vapor in the gas phase. The flux of metallic vapor from pressure may be neglected because there is no pressure gradient. There is no flux from convection because there is no net flow of gas within the metal-aggregate system, and thermal diffusion is negligible compared to the flux from ordinary diffusion. If the material being studied is allowed to vaporize until steady-state behavior is attained, the experimental results may be analyzed using Fick&apos;s First Law.

Jan 1, 1970

By Garth M. Crosby

Hugh E. McKinstry (Professor of Geology, Laboratory of Mining Geology, Harvard University, Cambridge, Mass.) Pre-Cambrian age for the Coeur d&apos;Alene mineralization, as indicated by isotope studies and recently discussed by Silverman, Long, and Kulp&apos; would explain some features of the mineralogy of the district that have long been a puzzle. In the Silver Belt, especially in the Sunshine mine, lead-zinc min erali zation passes downward into tetrahedrite ore. Although commercially speaking this is a rich silver zone, the silver is, quantitatively, a mere impurity amounting to a small fraction of 1 pct. In effect the zonal change is from lead-zinc down into copper mineralization—-the usual zonal change that occurs in many districts. In the Burke-Mullan portion of the district, on the other hand, lead-zinc ore does not pass downward into copper mineralization of the Sunshine type. Instead, pyrrhotite appears in depth while the tenor in lead and zinc declines. The change occurs at increasingly greater depth away from the Gem stocks, deepening irregularly by some 3000 ft within two to four miles. As noted by Crosby, biotite, grunerite, and garnet appear in the deep zone. The marked difference between this apparent zonal change and the more nomal change to a copper zone is quite explainable if already existing pre-Cambrian veins have been locally metamorphosed by a Tertiary intrusive. The chief obstacle to this explanation is the evidence that mineralization cuts Laramide intrusives, but evidence on this point is conflicting as indicated by Crosby&apos;s observations and summary. This is not the first instance of a problem in determining the time-relationship of mineralization to a spatially associated intrusive. At the Noranda mine veins of chalcopyrite extend into a diabase dike which apparently cuts the ore, although Price2 concludes that the ore is later. However, at the Normetal mine diabase of a similar dike is thought3 to intrude the orebody but is cut by stringers of chalcopyrite. In the Sullivan Mine, B. C.,4 galena follows a fracture in a larnprophyre dike which, itself, cuts the main orebody. In the Sudbury district dikes of olivine diabase are clearly younger than the nickel ore, yet where they cut the Creighton orebody they contain stringers of chalcopyrite. In the laboratory, Hawley5 has developed veinlets of sulfide (chalcopyrite) it] silicate gangue by heating specimens of ore in a stream of H2S at 410 °C. From this and other evidernce. it seems clear that sulfides can be transferred from one site to another — at least through short distances — at temperatures well below their melting points. It would seem then that even if sulfide Mineralization in the Gem stocks can be shown unequ ivocably to be later than the intrusive the possibility of "remobiliza tion" need not be more than local. Thus the zonal relationships are quite in accord with a pre-Cambrian age for original deposition of the lead, zinc, copper, silver, and uranium in the Coeur d&apos;Alene district. REFERENCES 1. A. Silverman, A. Long, and J. L. Kulp: Discussion of: The Gem Stocks and Adjacent Orebodies, Coeur d&apos;Alene District, Idaho. Mining Engineering, May 1960, pp. 470-471; AME Trans., 1960, vol. 217, p. 117. 2. Peter Price: Geol. & O. D. at the Home Mine, Noranda, Quebec. Can. Inst. M & M Bull 263, 1934, p. 108; also,Trans. CIMM 1939, pp. 108-140. 3. w. L. Brown Nometal Mine in structural Geology of Canadian Ore Deposits, Montreal, 1948, p. 690. 4. C. O. Swanson and H. C. Gunning: Geology of the Sullivan Mine. Can. Inst. Mining & Met. Trans. vol. 48, 1945, p. 653. 5. J. E. Hawley: Heat Effects on Sulphides and Possible Applications. Univ. Toronto Studies, Geol. Ser. No. 46, 1941, p. 34.

Jan 1, 1961