Search Documents

By G. Ansel, J. O. Betteron

THE PURPOSE OF THIS PAPER is to give a brief picture of present day magnesium rolling practice, to elaborate on laboratory and development rolling experiments; and finally, to discuss the possible Future rolling of magnesium. The present production practice is so varied between various mills that it can only he concluded that no single producer is now using a process that is outstandingly superior to others. In view of this, only the general features of present day production practice have been presented and attention is focussed on the results of laboratory find development rolling of magnesium-base alloys as indications of the Future trend of magnesium rolling. MAGNESIUM ROLLING LITERATURE The literature relating to magnesium rolling is divided into three groups: the deformation mechanisms of the hexagonal magnesium crystals, the metallurgical aspects and laboratory type experiments in rolling, and finally, the articles on production rolling methods. This literature was reviewed and is summarized below. In the first group of references, the existence of basal slip in magnesium single crystals was shown by Schiebold and Siebel1 and of {102} twinning by Mathewson and Phillips2, Schmid3 predicted and partially established {101} slip at hot working temperatures. Bakarian and Mathewson4 confirmed the above and eliminated {101} twinning as a probable deformation mechan-

Jan 1, 1948

By Charles S. Barrett, L. H. Levenson

Plastic flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following fundamental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the 1attice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals —('grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by various investigators for more than 25 years, ‡ yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of material that was used in the earlier compression experiments1—hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By Carmine D. &apos, Lemuel Tarshis, Joel Hirschhorn, Antonio

Vapor-deposited nickel films in the thickness range 700 to 4360A were tested in uniaxial tension utilizing a microtester designed specifically for this study. Contrary to the findings of some investigators, a definite thickness-strength relationship was observed below 3000 A with a four-to sevenfold increase in strength over that of bulk nickel. The films were characterized by high elastic strains and little plasticity. On the basis of these and other reported data, it is suggested that the high strength level in metal films is related to the manner in which they are produced. Vapor deposition, owing to its severe quenching effect. is believed to promote the formation of point defects which inhibit dislocation movement. IN recent years it has been reported that metals, when in the form of thin films, exhibit extraordinarily high strengths. The data published to date have been primarily concerned with silver and gold because of the ease with which these metals can be vapor-deposited and their high resistance to surface oxidation. Previous investigations into the mechanical strength of thin films has uncovered an apparent dichotomy of view on film behavior. Beams and his co-workers have reported a definite dependence of strength on film thickness. Other workers,"-'6 however, in separate studies on the strength of poly crystalline and single-crystal films have found no such thickness-strength relationship. The study of thin-film strength is extremely difficult because of the many variables associated with film preparation, handling, and testing. Moreover, the manner of test employed by different investigators has varied quite radically, ranging from simple uniaxial-tension to biaxial-bulge testing. The work reported herein was conducted in order to determine the mechanical behavior of a structural metal when in the form of a vacuum-deposited thin film and to gain some insight into the reasons for the high strengths exhibited by metals having such a con- figuration. In this study a method of test was chosen which would yield results which are easily interpreted and lend themselves to comparison with properties of the same material in bulk form. Moreover, specimen-preparation parameters and film-handling techniques are set forth so that other investigators can properly compare their findings with ours. EXPERIMENTAL PROCEDURES A) Film Preparation. Vacuum deposition was performed in an 18 by 30 in. bell jar using a standard New York Air Brake Co. vacuum station with a 6-in. oil-diffusion pump. Before evaporation the system was pumped to a pressure of less than 2 x 10"5 torr. A shield was employed to protect the substrates from the emission of contaminants during the critical melting and outgassing of the evaporant. The source consisted of from one to six filaments (0.020 in. diam). The length of each filament was about 5 in. and was placed 6 to 8 1/2 in. from the substrate in such a manner that the substrate face was at 90 deg incidence with respect to the evaporant beam. The temperature of the source was 2000"~ during evaporation. The films were deposited onto a substrate arrangement which was composed of four basic components, that is: 1) a 3 by 1 in. glass slide; 2) a 22-mm sq micro cover glass on 1); 3) a 22 by 50 mm micro cover glass coated with collodion on 1); and 4) a stainless-steel sheet mask containing twelve rectangular openings of 1-mm and 2-mm widths and lengths of 5 mm laid over 3). Thus, test specimens of 1-mm and 2-mm widths are deposited onto a collodion substrate which precludes epitaxial effects in the specirnens. 17-le The rectangular cover glass and square cover glass were positioned in such a manner that a strip of film would be evaporated along the length and across the width of the large glass slide. This boundary of evaporated film was used to determine the film thickness by multiple-beam interferometry. The square cover glass was used for X-ray and chemical analyses. Thickness of the deposits was varied by changing the number of filaments used (one to six). The duration of evaporation was 30 sec for each filamgnt which resulted in a deposition rate of 8 to 20A per sec. Evaporations were all performed at room temperature; however, radiant heat from the source raised the substrate temperature to 40" to 60°C. All substrates were cleaned by ultrasonic agitation in a solution of spectranalyzed isopropyl alcohol. Collodion was deposited on the micro cover glass by immersion in solution of collodion in amyl acetate. B) Thickness Control and Measurement. Film

Jan 1, 1963

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,' the gold film marker of Kofstad and ~jijllesdal,' and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.' reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

By V. Jares

DESPITE the fact that a combination of metals-aluminum-zinc-tin, and sometimes aluminium-zinc-cadmium-is extensively used for aluminum solders, as well as for die-castings, the constitution of these alloys has not yet been made clear. I. BINARY SYSTEMS The system aluminium-zinc is the basis of the ternary alloys under consideration. Their composition was made sufficiently clear by the investigations of Roscnhein and Archbutt,1 Bauer and Vogel,2 Sander .and Meissner,3 Hanson and Gayler4 and Isihara.5 Only the temperature of decomposition of the crystals s seems still to be doubtful, whether it is considered as a compound of Al2Zn3 (according to Bauer and Vogel) or as an intermediate phase of variant composition (according to Hanson and Gayler). This temperature is given by most of the authors, as in the neighborhood of 256° C., only Isihara giving 280° C. As its accurate determination is of special importance in the study of the ternary alloys under consideration it was experimentally controlled in the following manner: An alloy corresponding in composition to the formula Al2Zn3 was made, in which the temperature effect was found to be the greatest. This was drilled and a silver-constantan thermoelement inserted into the cavity so as to be in direct contact with the alloy. The whole was then very slowly heated and the heating and cooling curves determined. The transition temperature from the heating curve was found to be 281° C., whereas-from the cooling curve it was 252° C.

Jan 10, 1926

By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

By Charles S. Barrett, Robert F. Mehl

A study of the structures arising from the decomposition of the ß solid solutions in the Cu-Zn and the Cu-A1 systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution— the Widmanstätten structure—-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the ? phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series—that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-—which at present seems the only a1ternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the ß and in the precipit'at.ion of the y phase from the y in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point, of view.

Jan 1, 1931

By K. C. Strebig, C. W. Schultz, A. A. Selim

The effect of some organic additives in diamond drilling of quartzite was investigated in the laboratory. The drill was designed to measure the rate of penetration, the thrust, and the torque and to record each as a function of the distance drilled. A statistical plan was followed throughout the investigation and an equation representing the bit performance was derived from the mathematical theory of reliability. The drilling torque was found to increase with the use of additives while the sliding coefficient of friction and the wear coefficient decreased. The energy per unit volume consumed was found to increase with the use of additives. A hypothesis explaining the effects achieved with the additives is given. INTRODUCTION For some time researchers have attempted to increase drilling efficiency by adding certain agents to the flushing medium. Much of this interest is the result of the observations of Rehbinder, Shreiner and Zhigach1 They postulated that "...in processes for the mechanical destruction of solids, a region of increased crack formation is created in the deformed layers adjoining that surface of destruction, forming the predestmction zone. The surrounding medium (for example, a liquid) which wets a given solid will penetrate the embryo microcracks of the predestruc-tion zone. Increasing the molecular affinity of this liquid for the surface of the solid considerably facilitates the deformation and destruction by softening the solid in the zone of increased crack formation. In this manner, the hardness or strength of the deformed body is decreased by the influence of the penetration of the liquid into the predestraction zone." This is known as the "Rehbinder effect". Rehbinder's work has prompted many investigators to examine the effect of additives on the mechanical destruction of rocks. Engelmann, Terichow and Selim reported that the maximum penetration of the rock by a diamond point in a solution environment was at the isoelectric point of the solution.* Robinson reported that his results did not appear to support the theory of Rehbinder.3 Joris and .McLaren suggested that additives with surface tension lower than water will be more efficient in cooling the diamonds.4 Their effectiveness in removing the fine cuttings from the face of the bit will also improve the efficiency of the system. They reported an improvement in impregnated bit life and penetration rates with the use of soluble oil additives. In contrast, Long and Agnew, drilling with surface set bits, reported that lubricating agents increase bit temperature and wear.5 A significant change was reported6 in the mechanical properties of rock with polar additives. It was concluded that this change in the mechanical properties of the rock in the presence of the additive is due to the rock hydrophilic properties. Ethylene glycol, glycerine and anionic detergent were selected for this investigation because their surface tension is lower than that of water. The surface tension of these additives for the concentrations studied was 42 to 75 percent of the surface tension of water. A low surface tension additive would wet the surface of the diamonds more easily and hence would be more effective in cooling the diamonds. Another characteristic of these low surface tension additives is their effectiveness in removing the cuttings and preventing the flocculation of the formed particles in the drilling process. This article summarizes the results of an investigation performed at the laboratories of USBM, Twin Cities Mining Research Center. The objective of the investigation was to study the over-all effects of some organic additives on the performance of diamond impregnated bits in atmospheric drilling conditions only and not in downhole pressured conditions.

Jan 1, 1970

By Roger L. Beals, George A. Tweedy

The results of the cyanide-operations, given in detail in the following paper, show the progress that is being made at the Minas del Tajo. The old pan-amalgamation process, in operation up to and including 1905, while paying a profit on high-grade ores, was no longer able to treat profitably the ores in sight at that time; hence an alteration in the process was imperative. The success of this alteration is eloquently expressed by the following data : Pan-Amalgamation. Cyanidation. 1905. 1905. " 1908. Tons treated,.... 51,387 58,983 69,200 Value per ton (U. S. currency),. $ 10.78 $8.39 $8.28 Extraction, per cent.,.. 65.00 88.56 87.45 Extraction, per ton,.. $7.00 $7.43 $7.24 Total cost, per ton treated, . 6.50 4.36 4.01 Profit, per ton treated,.. 0.50 3.07 3.23

Jan 1, 1911

By J. O. Nelson, C. J. Altstetter

Single crystals of hcp cobalt, 3 mm in diameter and up to 35 cm long, were grown using an electron-beam, zone-melting technique. The martensitic-phase transformation was studied in single-crystalline and polycrystalline specimens by making length-change measurements as a function of temperature under various elastic compressive stresses. Upon thermal cycling, single-crystalline or polycrystalline specimens repeatedly transformed almost entirely on the same variant of close-packed plane provided the maximum temperature did not exceed 600°C. Cycling to 1000°C resulted in transformation on more than one {111} variant. This behavior is termed multivariance. The multivariant transformation occurred very rapidly at an M, temperature 2° to 6°C lower than the M, of a transformation which would result in a single-crystal product. Elastic compressive stresses (up to 253 g per sq mm) tended to lower the A, and raise the M, temperatures, decreasing the width of the temperature vs dilatation hysteresis loop. The transformation habit plane and transformation shear direction of an as-grown single crystal were not grossly affected by elastic compressi?ie stress. This was evidenced by similar dilatations on the temperature us dilatation loops joy specimens with and without compressive stress. A dislocation mechanism is proposed to explain the observed results. IT has been shown that, on heating, cobalt transforms martensitically from the hcp to the fcc phase.' The transformation habit plane is (0001)hcp || (lll)fcc and the transformation shear direction is (1010)hcp || (112)fcc. The transformation involves a shear of 1g°28', which may be achieved by a shearing of a/6(112) of every two planes with respect to the plane beneath, thus changing the ABABAB stacking of hcp to the ABCABC stacking of fcc. Associated with the phase change is a 0.3 x 10"3 contraction in the habit plane and a 4.2 X 10"3 expansion perpendicular to the habit plane resulting in a 3.6 x X volume increase on heating.' On cooling, an identical volume decrease takes place. The temperature at which the fcc phase begins to form on heating (A,) is reported as 430°C, and the temperature at which the hcp phase begins to form on cooling from an elevated temperature (A&) is reported as 390oC1,3 Consequently, temperature vs dilatation plots have the form of a hysteresis loop. If heating or cooling is reversed during a transformation, a smaller hysteresis loop results. Upon heating, the transformation is always complete; whereas, fcc is often retained at room temperature as a metastable phase entrapped in the polycrystal-line hexagonal matrix.1,4,5 Two obstacles in the theory of the allotropic-phase transformation of cobalt have been: 1) a detailed knowledge of the product nucleus, and 2) a plausible method of propagation of the transformation. Bilby,8 christian, 7 and seeger 8,9 have suggested a "pole mechanism" as a means of propagation of partiai dislocations from plane to plane. A pole dislocation and a Shockley partial come together at a node. The a/6(112) Shockley partial rotates about the pole dislocation effecting the transformation shear. The pole dislocation must have a 2a/3(111) screw component which causes extension of the transformed region by two atomic planes with each full rotation of the Shockley partial. Bollmannl0 suggested, on the other hand, that transformation propagation occurs due to the stress fields of intersecting (111)-type stacking faults. As faults intersect, a stress distribution is set up about their intersection which is in turn reduced by the emergence of another fault on the second nearest plane. This process continues with the final result of a complete phase transformation. In view of the similarities between deformation and transformation in cobalt, the effect of stress on the transformation would, hopefully, yield valuable information concerning nucleation and propagation. In the present work single-crystalline and polycrystalline specimen length changes were measured as a function of temperature at various compressive loads. PROCEDURE Several orientations of single crystals of hcp cobalt in lengths up to 25 cm were grown by electron-beam floating zone melting from 99.95 and 99.999 pct, 3-mm-diam cobalt rod as supplied by Johnson

Jan 1, 1964

By J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959

By S. S. Clarke

LATE in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls Were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1947

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan&apos; investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0&apos;~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther&apos; investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By Warren Howes, C. O. Anderson, Robert E. Illidge, M. D. Harbaugh, S. J. Burris

The Tri-State zinc-lead mining district embraces an extensive area, including the northeastern part of Ottawa County, Oklahoma, the southeastern part of Cherokee County, Kansas, and adjacent portions of Missouri, mainly in Jasper County. The Oklahoma-Kansas portion of the district, in the vicinity of Picher, Okla., has been the principal producing area since 1917, and the present milling practice in that section is the subject of this paper. This district is the largest zinc-producing field in the United States. In 1926 it produced 55 per cent of the nation&apos;s zinc and 15 per cent of its lead, and in 1933 it produced 35 per cent of the zinc and 10 per cent of the lead. From 1842 to 1933, inclusive, the total output of the district was 18 1/2 million tons of zinc and lead concentrates valued at 818 million dollars. Of this production, the Oklahoma-Kansas, or Picher, field yielded over 9 million tons valued at over 400 million dollars. Mining operations in the Oklahoma-Kansas field near Picher and Baxter Springs began in 1915. The mills built it that time consisted merely of gravity concentration plants employing jigs and tables and the same flow sheets as had proved satisfactory with the free-milling ores such as were mined in the Joplin-Webb City fields in Missouri. The Kansas-Oklahoma ores proved to be much richer but also more refractory to treatment than those in the Joplin area, and contained a considerable percentage of zinc mineral not freed by the amount of crushing usually practiced in preparing the ores for jigging. Thus the old Joplin type of mill, with its usual two or four jigs and a few tables, proved inadequate and resulted in excessive tailings losses sometimes as high as 50 per cent

Jan 1, 1935

By M. A. Jones

Performance of a pilot flood in eastern Kansas indicates improved recovery and accelerated production resulting from mobility ratio control obtained by adding a high moleculur weight polymer to injected water. Ultimate pilot flood recovery of the 75-cp reservoir oil is anticipated to he 350 bbllacre-ft during the six-year flood life. Cumulative recovery to date totals 242 bbl/acre-ft after 30 months of injection. Reservoir parameters and flood performance are disc~rssed in detail to provide a case history relating to the feasibility of polymer flooding. INTRODUCTION The Vernon Polymer flood of the Brazos Oil & Gas Co., located in Sec. 2, 24 S., 16 E., Woodson County, Kans., was begun in late Oct., 1963. Injection of a 500 ppm solution of Pusher* polymer was initiated in a 15-acre pilot to determine feasibility of improving oil recovery by mobility ratio control. Performance to date and the anticipated recovery of 115,000 bbl from the 329 acre-ft pilot indicate efficient displacement of the viscous reservoir oil. Dependence of flood recovery on the displacing fluid-displaced oil mobility ratio has long been recognized. Displacement efficiency of the reservoir oil decreases with increasing mobility ratio. Therefore, economic reduction of this parameter is an attractive approach to improving oil recovery. particularly from viscous oil reservoirs where mobility ratios are often quite high. Waterflood mobility ratios can be controlled by dilute solutions of certain polymers&apos;; which provide a displacing fluid with considerably reduced mobility. Reservoir parameters and flood performance are emphasized in this paper to provide data relating to polymer flood applicability. THEORY The polymer used in the Vernon pilot exhibits the property of unusually high resistance to flow through porous media.&apos;.&apos; A small concentration in injected water effects a mobility reduction considerably beyond that predicted from increases in bulk viscosity as measured in a capillary or rotating cup viscosimeter. Water mobility in the subject flood is reduced by a factor of 7.55 with the addition of 500 ppm Pusher chemical to injected water while the bulk viscosity is increased from 1.03 to only 1.40 cp at 75F. The exact flow mechanism causing resistance to flow has not been established; however, it is observed only in tortuous flow systems and appears to be influenced by brine properties, rock properties and oil saturation. Consequently, mobility reduction is estimated from flow studies for a given sample of reservoir rock and is expressed in terms of a "resistance factor".&apos; This parameter is defined as the ratio of brine mobility to polymer solution mobility measured at residual oil saturation: RF= ?m/?p= (km/µm)/(kp/µp)M.......(1) where RF = resistance factor (dimensionless) k*. and A, = mobility of water and polymer solution, respectively k,,, and k,, = water and polymer permeability, respectively (darcies) µie and µp = viscosity of water and polymer, respectively (poise). Eq. 1 is similar to the expression commonly used to relate the relative mobility of the water bank at residual oil saturation to oil-bank mobility at irreducible water saturation: where M =mobility ratio of water to oil (dimension-less) A, = mobility of oil k, = permeability to oil (darcies) )i* = oil viscosity (poise). From Eqs. 1 and 2 it is apparent that the polymer-solution-to-oil-mobility ratio can be approximated by dividing the brine-to-oil ratio by the resistance factor RF: Mpn=M10/RF...........(3) where M,-, = mobility ratio of polymer solution to oil (dimensionless). This simplified presentation assumes no dilution of the polymer solution by connate water. Also, the presence of a connate water bank separating the polymer solution from the displaced oil is not considered. Displacement of oil by waterflooding is increasingly dominated by viscous forces as the viscosity of the oil displaced increases. When the oil mobility is less than that of the injected water, the oil-water interface is not a piston-like front.3,&apos; Instead, instabilities occur at the flood front in the form of viscous fingers which tend to penetrate the less mobile oil bank. The magnitude of these protrusions, or the degree of channeling, increases

Jan 1, 1967

By G. W. Preckshot, N. G. DeLisle, C. E. Cottrell, D. L. Katz

MOST crude oils contain asphaltic substances that may be naturally or artificially precipitated. In the Greeley field, California, this asphaltic bitumen is precipitated during the flow of the oil from the reservoir to the stock tank. The mechanism of such precipitation is not well understood. This paper presents the progress that has been made by using the electron microscope as a new tool and by observing the effects of the streaming potential on the formation of bitumen particles. Crude oils at atmospheric pressure viewed in the electron microscope in very thin films under a vacuum showed no asphaltic particles. A technique of preparing slides of thin films by dilution of the oil with benzene and washing in petroleum ether was used at first, and these observations showed that the solvents caused the formation of the particles, varying from 0.01 to 0.2 micron in diameter. The electrical effects of fluids flowing through porous solid were studied, with emphasis on the formation of colloidal particles by the streaming potential. The streaming potential of crude oil flowing through sand was measured and was shown to be responsible for the formation of bitumen particles. These results bring out a new phenomenon, which may occur when crude oil flows through the porous oil reservoir.

Jan 1, 1942

By Frank F. Poland

TEE purpose of this paper-is to describe a new process for the refining of secondary copper-base metals and a specially designed high-temperature electric-resistor furnace used in the process for the distillation of zinc from these metals. The process was used for the conversion of nickel silver to cupronickel and to recover the zinc content in metallic form. It also proved applicable and economical for the treatment of scrap brass for separating and reclaiming the copper and zinc. The relatively large furnace developed for the distillation of zinc is described in detail, for it made economically possible the direct recovery of metallic zinc from scrap brass, which is a new step in the processing of such material. Considerable interest has been shown in the utilization of the distillation furnace for other metallurgical processes, where it is of advantage to operate in a controlled neutral or reducing atmosphere, or to avoid having the processed metal in contact with refractories other than carbon, or to operate at temperatures between 3000 and 4000°F. PURPOSE OF DEVELOPMENT It was recognized early in the war effort that nickel would become a critical metal, therefore all nickel stock and alloys containing relatively high percentages of nickel were frozen immediately. Among these alloys were considerable quantities of various grades of nickel silver, an alloy containing copper, nickel, zinc, and in some grades lead, also minor amounts of iron, manganese and other constituents. At the time there was no existing plant or process to eliminate the zinc, lead, and minor constituents so as to convert this metal to cupronickel, one of the important alloys needed by the U. S. Navy for condenser parts. Therefore the Bureau of Industrial Conservation of the War Production Board requested the executives of the leading nonferrous metal companies to have their metallurgical staffs study the problem of converting this metal to cupronickel conforming to U. S. Navy Specification 44T40. The composition specified therein is as follows: nickel, 29 to 32 per cent; zinc, 1.00; iron, 0.00 to 0.60; lead, 0.05; tin, 1.20; manganese, 0.00 to 1.00; total of other elements (maximum), 0.50; copper, remainder. The problem in converting these alloys to cupronickel was the elimination of zinc, lead, iron, manganese, and other elements without appreciable loss of nickel to slags or other by-products. Revere Copper and Brass Incorporated, through its Research and Development Department, undertook to solve this problem. A Government-owned plant was built at Rome, N. Y., and there the con- version was successfully made.

Jan 1, 1946

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.&apos; The porous-pellet model is found to give a better description than the dense-pellet one for McKewan&apos;s measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.&apos;&apos;&apos; However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.&apos; One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed&apos; to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak&apos;s4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis&apos; solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953

By R. H. Hadfield

Professor ArnolD, of the Sheffield Technical School, who has done so much excellent work in metallurgical research, recently produced, with the aid of aluminum, a sound ingot and bar from the purest known Swedish brand containing 99.8 per cent. of pure iron. Table 1. shows the physical quantities of this metal. TABLE I.— Tests of a Sample of Almost Pure Iron Prepared by Professor Arnold from D. v Ewedish Bar, Containing Before Fusion 0.04 Per Cent. of Carbon. I. II.+ III. Series mark,.. 136 1.371F ...... C, 0.07 0.07 Si, 0.04 0.04 8, 0.02 0.03 ...... Analysis, per cent,. .. P, 0.02 0.015 ...... Mn, 0.06 0.07 Al, 003 ............ Fe, 99.76 99.81 ...... Specific gravity,........... 7.863 ...... Original diameter, inches,. .. 0.564 0.798 0.798 Original area, square inches,. . 0.25 0.50 0.50 Limit of elasticity, tons per square inch,...... 18. 3.8 Breaking-load, tons per square inch,. 21. 23. 14.75 Total elongation, per cent., measured on 2 in.,...... 50. 49.25 61. Total reduction of area, per cent.,. 80. 69.60 61.20 Extension at permanent set, per cent.,...... 0.007 ...... silky and Appearance of fracture,. .. . silky i granular in parts.

Jan 1, 1894