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By B. C. Allen

The solubility of chromium in liquid silver and that of molybdenum and tungsten in liquid tin have been determined by equilibrating Ike Liquid in a crucible of the solule metal. Generally the weight of solute in solulion was delermined both chemically and from crucible weight losses. The resulting weight percent solubilily of chromium in silver as a function of absolule temperature T is given by log w = -6660/T + 4.02 in the range 960° to 1445°C, and that of molybdenlttrl in tin by log w = —5050/T + 1. 79 in the range 1200° to 2200°C. The values appear unaffected by minor changes in solute composition. Calculations aye made of the parlial molar heal and excess entropy of mixing. The estimated solubility of tungsten in tin is 0.001 pct at 2000°C. Evidence is presented that molybdenwm dissolves in tin without compound for mation and that tungsten and tin form W10Sn. RECENT developments in coatings, heat transfer, and brazing require a knowledge of equilibrium solubilities in a variety of systems at elevated temperatures. Of particular interest are solid-liquid interactions in metal systems involving dilute solutions. This investigation was undertaken since little is known about the phase relations or solubility of chromium in liquid silver or of molybdenum and tungsten in liquid tin.1,2 EXPERIMENTAL WORK As indicated in Table I, high-purity metals or those of known impurity levels were used. Crucibles were machined from chromium, molybdenum, and tungsten bar stock 1.3 cm diam and 2.2 cm long. Chromium rod was prepared by arc melting and extruding iodide process crystals.3 The five chromium impurity alloys were in the form of 0.6-cm-diam swaged rod. A Cr-0.06N* alloy was prepared by exposure to NH3 at 1150°C in a closed quartz capsule for 24 hr. Because significant nitrogen was lost during annealing in argon at 1600°C,4 the estimated level was 0.01 pct N. Chromium and Mo,W crucibles were outgassed at 1200" and 1600°C, respectively, at 3 X 10-5 mm. The solvent was placed In crucibles of the solute metal- 6 g Ag in chromium, 0.4 g Ag in the five chromium impurity alloys, and 4 g Sn in Mo,W crucibles. The silver and tin series were outgassed at 900" and 110O°C, respectively, and held at the desired solution temperature in a tantalum resistance furnace under 1.05 atm 99.995 pct Ar. An equilibration time of 0.5 to 1 hr was chosen since 0.3-, I-, and 4-hr anneals at 1235°C for Cr-Ag yielded similar results. Temperatures were measured optically to +10°C under essentially black body conditions which were checked against the melting point of silver. The Cr-Ag and Mo-Sn,W-Sn series were respectively equilibrated at 990° to 1400°C and 1200" to 2000°C. Vaporization losses were generally held to <1 pct by the argon. In the 1800" and 2000°C anneals for 0.5 hr, the crucibles were placed in tightly sealed tantalum cans which kept tin losses to <5 pct. After the anneals, the specimens were furnace-cooled. One anneal was made on small Mo-0.02 C, Mo-0.5Ti-0.lZr, and tungsten crucibles containing tin at 2200°C. The metals were sealed in an electron-beam-welded tantalum can of minimum volume. After the anneal, tin was still present in each crucible, none of which was severely attacked. After equilibration, the saturated solvent metal was selectively removed from the crucible by acid leaching. Weight losses sustained by the crucibles were determined from the initial weight minus the final blank-corrected weight after acid leaching. Chemical analyses were performed on some of the samples. Hot 1:l HNO3-H2O removed silver from chromium with the blank running <0.1 mg or <0.002 pct on measured solubility. Tin was removed from molybdenum and tungsten by hot concentrated HC1 with the respective blanks amounting to -0.004 and -0.0004 pct in the presence of tin. The insoluble residues were weighed and checked for composition. The leaching solutions contained traces of the solute metals which were analyzed by colorimetric methods, Diphenyl Carbazide for chromium, Thiocyanate for molybdenum, and Dithiol for tungsten. The total of the two percentages found from the residue and leaching solution minus the blank gave the desired solubility values. On the basis of annealing empty molybdenum and tungsten crucibles, weight losses due to MoO3 or WO3 volatilization were found to be generally 10.4 mg and affect measured solubilities by <0.01pct. RESULTS AND DISCUSSION Chromium-Silver . Since no intermediate compounds are reported to form in the Cr-An system,&apos; crucible weight losses and chemical analysis of the entire melt should provide reliable measures of the chromium in solution. Values obtained by the two methods are in agreement as shown by the results for unalloyed chromium in Table II and plotted in Fig. 1. Furthermore, the results are consistent with those previously determined by melting equilibrated silver out of the crucible and analyzing calorimetrically for chromium.&apos; On the basis of limited thermal analysis data, the solubility of chromium in silver has been quoted as 8 pct at the monotectic temperature of -1445°C.1 This investigation indicates an extrapolated solubility of 1.38 pct which is believed to be more reliable. At the eu-

Jan 1, 1968

By Solange Kazue Utimura

As placas de circuito impresso (PCIs) dos resíduos eletroeletrônicos (REEEs) possuem diversos metais na composição. A recuperação desses metais tem incentivado as pesquisas inovadoras no seu processo de extração. Como alternativa de recuperação de metais das PCIs de forma sustentável optou-se pela biohidrometalurgia envolvendo a fase extração. O presente trabalho avalia a biolixiviação do cobre na presença de duas cepas bacterianas distintas em PCIs de REEEs provenientes de impressoras obsoletas. As PCIs foram caracterizadas mediante as técnicas analíticas de espectrometria ICP-OES e de fluorescência de Raios X (FRX) para determinar os elementos químicos presentes na amostra inicial. As cepas utilizadas na lixiviação bacteriana foram Acidithiobacillus ferrooxidans (AF) e Leptospirillum ferrooxidans (LF), cultivadas em meio de cultura T&amp;K. Os ensaios de biolixiviação foram realizados em incubadora orbital, com velocidade de rotação de 170 rpm, temperatura de 30 oC, volume de inoculo de 10% (v/v) e densidade de polpa de 30g/L. A técnica empregada na concentração de cobre da solução após a biolixiviação foi a FRX. Foi possível determinar que a cepa AF apresentou uma extração de 100% de cobre em 8 dias em comparação com a LF na qual foi observado que a extração de cobre foi de 100% em 5 dias.

Oct 30, 2017

By D. B. Dow

In collecting and dissctinating inforr:.at'ion on ir.:,provec.. practices us0i in the pr eduction cf petroleur:1 and in the r;:;.:.1.nuf __ cture of gasoline, the Bureau of Mines ha.s aidei in creatin5 an interest i-n efficient 11:ethods in all phasas of tr.e oil ani gi:i.s iniustry. In the refinin£ ir...mstry ther.:: is a growing tend.ency for incre.:l.sea. effi. ,:;iency, ana inforr;.Eition rela:tin!s to ic:;p·roved practices should be of value not only to the larger and. core efficient plants, but particularly to srr.a.11 refineries unable to carry out a lar6e experLnental pro!§.rarn. The refi?eries of the United States required 4.3,915,029 barrels cf crude oil J.uring the year 1920*, inclu.::.in1:, 611136,210 barrels of Mexican cru::...e. This yielded. 4,8821546,599 gallons of E>asoline, a.n avara.t;,e ciaily pro;.iuct1on of 13,340,291 e,allons·, Besides the easoline obtainel fro;., cruie· oil by-fr:;.cticna.1 distillation and. from heavy oils by crackini:,, this a,-r;ount incluC1.es 3,152,924 bar­rels of natural-ga.$· gasoline blended. With asoline fro,., th otha two sourcs.

Apr 1, 1922

By Erwin Pink

It has been pointed out in a previous publication&apos; that, for a given strain rate, serrated yielding can be observed only at certain test temperatures. Fig. 1 shows the results obtained for polycrystalline and re-crystallized tantalum, Va group in the periodic table of elements, where serrations in the course of deformation match the decrease of total elongation. However, there was no evidence of repeated yielding when testing molybdenum or tungsten, VIa group, at similar conditions, i.e., annealed and air-cooled samples (serrations have been found in quenched tungsten2). The reason for the observed serrations in the stress-strain curve are dissolved impurities on interstitial sites of the lattice. Of importance is the concentration of oxygen, carbon, and nitrogen, which are in random solution. Two methods to calculate the limiting concentrations for serrated yielding have been evaluated and applied with more or less success in estimating the role of carbon and nitrogen in mild steel.3 J. Friedel4 has given two equations, which determine the upper and lower strain rates i for the appearance of serrations at a certain test temperature: W denotes the binding energy of the interstitial atom, -1 ev for refractory metals;5 e&apos; the portion of continuous strain in the discontinuous stress-strain curve, measured as -3x10-3; b the Burgers vector, c the concentration, see Table 11, in atom fractions; p the dislocation density, -2 X l09 per cm2 at an average stress ?, -15 kp per mm2 at medium strain. k stands for the Boltzmann constant, T for the absolute temperature, and D for the diffusion coefficient. Table I. Eq. [1], for a given strain rate, determines the minimum temperature, and [2] the maximum temperature, below or above which no "dynamic strain-aging" can occur. According to the calculation, which uses the given quantities, serrations should only be observed within the cross-hatched temperature regions in Fig. 1, and this is in good agreement with the experiment. The effect of varying impurity concentrations is indicated schematically in Fig. 2: only Eq. [I] is affected. Setting Eq. [I] equal to [2], one can calculate the limiting concentration cmin which first causes serrations. The second method uses the aging condition by Cottrell and Bilby6,7 \£i/ \ n. a / where n(t) is the number of impurity atoms, which segregate at a dislocation line of 1 cm length after the time t (t in our case is the time between "repeated yield drops" in the serrated curve, or, the time until the above mentioned strain E&apos; is obtained, i.e., -1 sec for medium intensity or serrations). no is the number of impurity atoms in 1 cm3 and A = Qb4ep[(1 + v)/(l - v)], derived from equations given in Ref. 7. p is the shear modulus, 18,800 kp per mm2 for tantalum, 12,200 for molybdenum, AE the tetragonal distortion caused by interstitial impurities in a bcc lattice (approximately 0.4 for both tantalum and molybdenum) and v Poisson&apos;s ratio (0.35 for tantalum, 0.30 for molybdenum). From Eq. [3], combined with the condition for a pronounced yield drop as formulated by cottrel16 (at least one impurity atom segregated at the unit length of a dislocation), again a no min, and hence the concentration Cmin can be calculated.

Jan 1, 1970

By Francisco Necy Alves Júnior

Os aços inoxidáveis superduplex (AISD) aliam boas propriedades mecânicas e resistência à corrosão, possuindo um vasto campo de aplicação na indústria petroquímica. Geralmente, os reparos dos equipamentos são realizados por soldagem, sendo importante a seleção de parâmetros. É de suma importância a obtenção do teor adequado de ferrita no metal de solda, sendo que a variação da energia de soldagem pode influenciar de forma direta a microestrutura e resistência à corrosão. Logo, este trabalho teve como objetivo avaliar os efeitos provenientes da variação de parâmetros de soldagem nas características do AISD UNS S32750. Foi avaliado o balanço de fases, relacionando esse efeito com a resistência à corrosão. Foram realizadas soldagens em chapas pelo processo TIG autógeno em 3 níveis de energia de soldagem (5, 10 e 18 kJ/cm), variando a corrente e velocidade de soldagem, de modo a obter 5 condições e a possibilidade de analisar as variáveis-resposta com essas variações isoladamente. A análise da microestrutura foi realizada por microscopia ótica e o teor de ferrita foi quantificado pela utilização de duas técnicas: ferritoscópio e quantificação por imagem. Foram realizados ensaios de temperatura crítica de pite para análise de resistência à corrosão. Concluiu-se então que o acréscimo de energia pela variação da velocidade de soldagem acarretou no aumento no teor de ferrita, ocasionando a redução da temperatura crítica de pite, sendo estes observados na fase ferrítica.

Aug 7, 2018

By M. Kitada, U. Kawabe, F. Ishida, T. Doi

The relations between micros tructures and critical current density in transverse magnetic field were experimentally investigated due to each transformation of the 0 to 0&apos; + P" phases at 700&apos; C for superconductmainly examined using replication electron microscopy. The ß&apos; or a precipitates were found to pin down magnetic flux lines in these alloys. The effects of precipitation upon the critical current density were discussed in relation with the size, spacing, and characler of these precipitates. HIGH magnetic field superconductors, such as Nb-Zr, Nb-Ti, and Nb-Zr-Ti alloys, have been recently put to extensive practical use as winding materials for superconducting magnets.13 The critical current density of these hard superconductors under an applied magnetic field is an important characteristic for magnet materials and is very sensitive to metallurgical structure. It is generally known that the critical current density is increased by introducing dislocations and precipitates into a superconductor; that is, dislocations and precipitates are presumed to be barriers that hinder quantized flux lines from moving.4&apos;5 Theoretical6&apos;7 and experimental analyses of the motion of flux lines and the interaction between flux lines and various defects have already been reported by many authors. Metallographic analysis of high magnetic field superconductors such as Nb-Zr and Nb-Ti is difficult, so that no quantitative relationship between microstruc-ture and critical current density has been established yet. In this paper, the effect of precipitation on the critical current density in magnetic field was investigated for two superconducting alloys, Nb-40Zr-10Ti and Nb-5Zr-60Ti. In these alloys the resistive critical field H, at 4.2oK was about 100 kG and the critical current density Jc at 80 kG was of the order of 104 amp per sq cm.13-l5 The superconducting properties were examined in relation to the microstructural changes due to transformation of i) the ß to ß&apos; + ß" phases at 700°C for Nb-40Zr-10Ti alloy and ii) the ß to a + ß phases at 500°C for Nb-5Zr-6OTi alloy. The effect of size, spacing, and character of precipitates on flux line pinning was in particular examined. The microstructures were studied by means of residual resistivity, microhardness, and tensile strength measurements as well as by X-ray diffraction, optical, and replication electron microscopies. I) EXPERIMENTAL PROCEDURE Pure niobium, zirconium, and titanium, in the form of rods 0.8 cm in diam, served as raw materials. Results of chemical analyses of these rods are given in Table I. Ingots of the alloys, 0.4 cm in diam and 3 cm in length, were prepared by means of levitation melting, utilizing a copper mold in an argon-gas atmosphere. Samples from the ingot then were cold-worked by grooved mill to 0.2 cm in diam, heat-treated homogeneously (in the ß phase region) for 5 hr at 1100° in a vacuum of 1 x 106 Torr, and finally cold-drawn to 0.025 cm in diam. For heat treatments, samples were wrapped in niobium foil and sealed in an argon-gas atmosphere in fused quartz capsules. Water quenching was done after each heat treatment. Subsequently H-J, were performed at 4.2° by slowly transporting the current through the samples 4 cm long, under transverse magnetic field, until the least detectable resistive terminal voltage was observed. The resistive critical field H, was taken as the field at which 100 pv appeared at 4.2°K across a sample 3 cm in length, with a current of 5 ma. The critical temperature T, was measured by means of a conventional four-probe resistivity technique and taken as the temperature at which the sample resistance reached one-half of full restoration of the normal-state resistance with a current l ma flowing through a sample 2 cm in length. Precipitates were observed by means of optical microscopy and carbon replication electron microscopy. The etching solution consisted of 5 ml HF, 10 ml H2SO4 10 ml H2O2, and 50 ml H2O, and shadowed carbon replicas were examined in a itachi HU-11 electron microscope operated at 50 kv. X-ray diffraction photographs were taken by a 11.46-cm-diam Debye-Scher-rer camera using copper Ka radiation. The micro-hardness was measured under a load of 200 g using

Jan 1, 1969

By W. S. McCain, B. A. Wilcox, A. H. Clauer

The creep and creep-fracture behavior of a Ni-200-2Th0, alloy has been studied over the temperature range 816° to 1038°C and stress range 4000 to 19,000 psi Specimens having their axes either parallel or transverse to the final sheet-rolling direction were tested in air, and the apparent activation energy for creep was found to be 92 kcal per mole, regardless of specinien orientation. The stress dependence 01- the steady-state creep rate, was satisfied by where n depended on orientation; n = 9.7 for rrzaterial transverse to the rolling direction and n = 24.3 for material parallel to the rolling direction. In the latter case, the relation was also valid. The rupture strength of material parallel to the rolling direction was -1.5 times gveater than the transverse rupture strength. Several tests in vacuum revealed that here the creep rate was higher and rupture life lower than for comparable tests in air. THERE is an increased interest today in producing improved dispersion-hardened alloys for high-temperature structural applications. This had led various materials designers to modify existing alloys, such as thoriated nickel. One system that has received considerable attention is based on chromium additions to Ni-ThO2, with the obvious motive of improving the oxidation resistance. Another effect of chromium is that of lowering the stacking-fault energy, y, of nickel. For example, the addition of 30 wt pct Cr decreases y from -225 erg per sq cm for pure nickel1 to -70 erg per sq cm.&apos; This decrease in y could have several effects on the deformation behavior. There is some evidence that cross slip of dislocations around Tho2 particles is a mechanism of tensile3 and creep4 deformation in TD Nickel (Ni + 2 vol pct ThO2) at temperatures below 0.5 the absolute melting point of nickel, T,. A decrease in ? by chromium additions should increase the difficulty of cross slip. Also it has been suggested that the high-temperature (T > 0.5Tm) rate-controlling creep process in "recrystallized" Ni-Tho2 alloys is the climb of edge dislocations over Tho2 particles.5 According to weertman6 a decrease in the stacking-fault energy should decrease the dislocation climb velocity resulting in a decreased steady-state creep rate. Thus, chromium additions to recrystallized Ni-Tho2 alloys would be expected to decrease the creep rate, all other conditions being constant. However, a difficulty arises when the stacking-fault concept is applied to high-temperature creep of dispersion-strengthened metals which are produced on a commercial or semicommercial scale. This occurs because the materials are processed so that they have a high-stored energy of cold work, and the other substructural effects could obscure any influence of stacking-fault energy per se. An example of an alloy with a high stored energy of cold work is TD Nickel bar. This material has a fibrous grain structure (1 I diam by 10 to 15 p long), and the structure is stabilized by the ThO2 particles. Annealing at high temperatures, e.g., 3 hr at 1300°C, causes no recrystallization or grain growth.4 Previous work by the authors4 showed that the high -temperature creep behavior of TD Nickel could not be related to any simple dislocation theory of creep, and this probably was associated with the complex initial structure of the material.

Jan 1, 1968

In 1991, US mine production of barite decreased 3.4%. Barite consumption, sold or used by grinding plants, decreased by 11.7%. Imports also decreased by 15.4% over 1990. World mine production increased I%, according to the US Bureau of Mines. The value of domestically produced barite, f.o.b. mine, increased 3.3% according to the Bureau. The declared value c.i.f. US port of all imported crude barite during 1991 increased from $40.61/t ($36.84/st) in 1990 to $42.35/t ($38.42/st), the Bureau stated. Nevada was the leading producer of barite with 78% of the total, followed by Georgia and Missouri. It is estimated that 75% of the domestically mined barite was used as a weighting agent in drilling fluids. The remaining 25% was used in barium chemicals, glass or as a filler. Most of the production from Missouri, Georgia and Tennessee was used in the non-oilfield sector. Of the total barite used by grinding plants and chemical manufacturers, it is estimated that 93% was used in drilling fluids. The remaining 7% was in the non-oilfield sector, including barium chemicals and fillers in paper, plastics and glass. Tonnage consumed in the drilling fluids market decreased due to the lower average rig count during 1990. The average number of rotary rigs operating was 860. That was 14.9% less than the 1990 average of 1010 in the US. Crude barite imports were 138 kt (152,000 st) less than 1990 or 15.4%. Imports accounted for 70% of the (ap¬parent) barite consumed in the US. During 1991, China continued to be the leading exporter of crude barite ore to the US with 85.1 %. India followed with 14.8%. About 97.5% of the imported barite ore was used in the oilfield sector. Ground barite imports decreased from 56.7 to 46.2 kt (62,500 to 51,000 st) 1991. Mexico was a major exporter to the US, accounting for 75.3% of the total ground barite imports. Canada shipped 23.7%, while other countries accounted for less than 1 %, primarily for the nonoilfield market. During 1991, the number of grinding plants supplying the drilling fluids market along the Gulf Coast was reduced from 12 to 10. Baroid Drilling Fluids completed its mining program at the Rossi Mine near Dunphy, NV.

Jan 1, 1992

By E. A. Gulbransen, K. F. Andrew

Weight loss measurements were made using a sensitive microbalance operating in a high vacuum system. The Langmuir equation was used to Calculate the vapor pressures of the several metals and alloys. Aluminum lowered the vapor pressure of i9,on in a 5.4 Al-94.6 Fe alloy, and of iron and chromium in a 4.8 Al-21.5 Cr-73.7 Fe alloy. The influence of oxide films formed on the alloys on the effective vapor pressures of the alloys was also studied. These studies were used to aid in the inte9,pretation of the high temperature oxidation of alloys based on iron, chromium, and aluminum. RECENT studies on the oxidation of chromium1 and the heat resistant alloy 5 Al-22 Cr-73 Fe showed transitions in the rate of oxidation at 900o and 1050oC respectively. The transition for chromium occurred at a temperature where the rate of evaporation of chromium from oxide-free surfaces equalled the rate of chromium atoms reacting with oxygen. This paper presents new vapor pressure studies on iron, chromium, and the specially prepared alloys 5.4 Al-94.6 Fe, 21.9 Cr-78.1 Fe, and 4.8 Al-21.5 Cr-73.7 Fe. The ternary alloy is similar in basic composition to the patented heat-resistant commercial alloy known as Kanthal. The binary alloys were studied to show the individual effects of aluminum on the vapor pressure of iron and of iron on the vapor pressure of chromium. The purpose of the proposed studies was to test the influence of metal volatility on the oxidation behavior of heat-resistant alloys based on iron, chromium, and aluminum. Since oxide films formed on the metal may limit metal transfer to the surface, the influence of oxide films on metal volatility was also studied. LITERATURE A) Vapor Pressure. The vapor pressure of iron has been studied by Jones, Langmuir, and Mackay,&apos; Dornte and Nrton. Edwards. Johnston. and Ditmar. and McCabe, Hudson, and Paton. Stull and SinkeT have calculated a heat of sublimation at 298° K of 99.83 kcalper g atom. The vapor pressure of chromium has been reported by Bauer and Brunner,&apos; Speiser, Johnston, and Blakburn, Gulbransen and Andrew,&apos;&apos; Vintaikin,o McCabe, Hudson, and Paton, and Kubaschewski and Heymer.12 Good agreement was obtained except for the early work of Bauer and Brunner.&apos; Stull and Sinke7 calculate a heat of sublimation at 298°K of 95.0 kcal per g atom. Vapor pressure measurements on aluminum have been made by Brewer and Searcy,13 Bauer and Brunner,aand Farkas.I4 Stull and Sinke,7 giving Brewer and Seary&apos;s&apos; data the most weight, derive a heat of sublimation of 77.5 kcal per g atom at 298 oK. B) Method. Two methods15 are used for measuring the vapor pressure of metals: 1) The Langhuir free evaporation method, and 2) the Knudsen effusion method, In the Langmuir method, used in the present work, the vapor pressure of the metal P is given by the equation: Here M is the molecular weight of the vapor species. T is the absolute temperature. (dw/dt) is the rate of sublimation in g per sq cm per sec and a is the condensation coefficient. a is a measure of the efficiency of condensation of molecules striking the metal surface from the vapor. If condensation results from each collision a is unity. This coefficient has been found to be unity,a, le for metals. These results establish the general validity of the Langmuir free evaporation method as applied to metals. EXPERIMENTAL A) Vacuum Microbalance Method. A modification of the Langmuir free evaporation method was used. Strip specimens were suspended from a sensitive microbalance operating inside of a high vacuum system. For alloys, microbalance methods17 must be used on large area samples at relatively low temperatures to minimize composition changes. The

Jan 1, 1962

By David Turnbull

IN isothermal recrystallization processes, new crystals generally grow into the matrix until they impinge upon other new crystals or an external surface, at constant linear rates G. Before impingement the perceptible course of growth can be described by the equation: 1 = G(t-7) C1I where, G = dl/dt, 1 is a crystal dimension measured in a constant direction, t is the time, and 7, the nucleation period, is a positive intercept on the time axis. Fig. 1 is a schematic representation of I as a function of time for a recrystallizing grain. G is dependent upon temperature, driving energy (strain or surface energy), relative grain and boundary orientations, but is generally independent of time. The frequency of nucleation, fi, (time" volume") can be defined by the equation: N = 1/fV [2] where ? is the mean nucleation period and V is the volume of the specimen that has not recrystallized. The kinetics of primary and secondary recrystallization generally can be described satisfactorily in terms of the parameters N and G only.&apos;-" After recrystallization is complete the average grain size 7 increases with time by "normal grain growth;" didt, the average rate of grain growth, is strongly time dependent and has not yet been precisely related to G for the motion of the individual grain boundaries constituting the system. It has been suggested4* " that the elementary act in grain boundary migration is closely related to the elementary act in grain boundary self-diffusion. Although the distance of atom movement in the two processes may be somewhat different, there is reason to expect that the activated states may be very similar, so that the free energy of activation for grain boundary migration should be of the same order of magnitude as for grain boundary self-diffusion. Therefore, it is desirable to develop a satisfactory basis for comparing data on self-diffusion and grain boundary migration and to make such comparisons where possible. Theory The formal theory of grain boundary migration rates is analogous to the theory for the rate of growth of crystals into supercooled liquids reviewed elsewhere 6-8. Boreliuss has shown that the latter theory describes, within the theoretical uncertainty, the growth of selenium crystals into supercooled liquid selenium. Motto and more recently Smolu-chowski" have derived expressions for the rate of boundary migration in recrystallization. The treatment to be presented is similar to Mott&apos;s excepting that the formalism of the absolute reaction rate theory will be used. The atomic mobility, M, in grain boundary migration is defined by: G = -M6p/6x where p is the chemical potential per atom and x is the coordinate measured in the direction of grain boundary movement. Let AF be the free energy difference per gram atom on the two sides of the boundary and k the thickness of the boundary. For RT>>AF the potential gradient across the boundary (6p/6x) is essentially linear and it follows that: SF/8x = - aF/N\ [4] where N is Avogadro&apos;s number. According to the Nernst-Einstein equation, M is related to a diffusion coefficient, Do, for matter transport in grain boundary migration by the equation: M = Da/kT [5] Substituting eqs 4 and 5 into eq 3 gives the basic relation between Do and G: G = DoaF/\RT [6] Do values may be calculated from experimental values of G from eq 6 and directly compared with the coefficient of self-diffusion within the crystal, DL, or the grain boundary self-diffusion coefficient D,. However, a more convenient, though equivalent, basis for comparing atomic mobility in grain boundary migration and self-diffusion is through the constants of the absolute reaction rate theory. According to this theory diffusion coefficients may be written:" D = k2(kT/h) exp [-AF,/RT] 171 aFa, the free energy of activation, is related to the measured energy of activation, Q, by the equation: AFA = Q - T aSx - RT [8] where aSa is the entropy of activation. Substituting eqs 8 and 7 into eq 6 gives: G = ek(kT/h) (aF/RT) exp [(AS,,)C/R] exp C-Qc/RTI C91 where the subscript G refers to boundary migration. The relationship between the driving free energy and the free energy of activation in boundary migration is indicated schematically in Fig. 2. Experience indicates that the variation of G with temperature can be described by: G= Go exp [- Qc/RT] [10] where Go and Qc are generally temperature independent over wide ranges of temperature. Comparison of eq 9 with eq 10 gives:

Jan 1, 1952

By Takeyasu Ito, Mayumi Someno, Kazuhiro Goto

SINCE the pioneering work by Kiukkola and Wagner,1 many experiments have been reported on solid electrochemistry at elevated temperatures. However, the studies have been confined to experiments under isothermal conditions. One may conceive many situations under nonisothermal conditions. With two different temperatures T1, and T2 at the two electrodes, the electromotive force, E of a Galvanic cell will be expressed by the following equation under a steady state heat transfer in solid electrolytes of zirconia-lime and thoria-lime. E = ^ $ l&-dGO2+a(T2-Ti) [1] where tO2- is the transference number of oxygen ions in the electrolyte, Go, is the chemical potential of oxygen, and a is the coefficient of the thermoelec-tromotive force due to the temperature difference. The objective of the present study was to evaluate the coefficient of the thermoelectromotive force for zirconia-lime and thoria-lime under isobaric condition. The physical meaning of this coefficient is out of the scope of the present communication. The experimental cell assembly is schematically shown in Fig. 1. The zirconia-lime electrolyte tube and thoria-lime electrolyte tube were 8.0 mm OD and 5.0 ID, from commercial sources with chemical analyses of 94.8 wt pct ZrO2, 3.85 pct CaO, 0.83 pct SiO2, 0.25 pct TiO2, and 0.05 pct Fe2O3; and 95.0 pct ThO2, 4.0 pct CaO and rare earth metal oxides, respectively. The specific gravity was 5.5 g per cu cm for zirconia-lime and 9.8 g per cu cm for thoria-lime. Original powder size before shaping and sintering the tube was several microns for both electrolytes. The distance separating the two electrodes was 4.0 or 5.0 cm. Platinum wire of 0.5 mm diam was used for the electrodes. The temperature gradient was controlled by heating one electrode with a small heating coil of nichrome wire. The temperatures at the two electrodes were measured with two calibrated Pt-13 pct Rh:Pt thermocouples, directly contacting the two platinum electrodes. The atmosphere was either air or pure oxygen. The partial pressure of oxygen in air was considered equal at the vicinities of the two electrodes, with negligibly small thermal segregation in the gas phase. The difference of the chemical potential of oxygen was controlled only by the temperature difference at the two electrodes and not by the oxygen pressure difference. The temperature ranges were 600" to 1200°C for zirconia-lime and 850" to 1200°C for thoria-lime electrolytes. Fig. 2 shows the relation of the measured electromotive force and the difference of the oxygen chemical potential at the two electrodes for zirconia-lime and thoria-lime electrolytes. The electromotive forces in the figure were measured by a *0.05 mv potentiometer. The chemical potential difference was calculated by the following equations.&apos;

Jan 1, 1970

By C. E. Morris, S. R. Pollack

Current -vo1tage -temperature characteristics were studied for Al-A12O3-Al, Au structures. The oxide film was grown by gaseous oxidation in an 0, glow discharge. The electron-transfer mechanism was identified as tunneling and the barrier heights and thickness were determined. It was found that the barrier height at the parent aluminum-oxide interface is 1.5 ev and the built-in vloltage with an aluminum counter electrode is 0.35 v. The growth mechanism of the oxide is also discussed and it is suggested that Mott&apos;s theory is not applicable in describing the growth. Discrepancies were observed in the detailed comparison of tunneling theory, based on a trapezoidal model, with the data, and several possible explanations are discussed. THEORETICAL analyses of electron tunneling from one nonsuperconducting metal to another through an extremely thin insulating film have been presented.1-6 These calculations relate the current density, J, to the voltage, V, between the two metals, and to the temperature, T. The results of these calculations indicate that the magnitude of J and the detailed shape of the J-V characteristic will in general depend most strongly upon such properties of the insulating film as the thickness, the dielectric constant, and the structure of the electron energy barrier profile. The experimental results of many7-11 workers have corroborated the main features of these calcu- lations and have in fact been used to determine properties of the thin insulating film. It has been demonstrated, for example, that the tunneling current formulation of simmons4 is adequate to describe the observed J-V characteristic over approximately 10 orders of magnitude of current. Furthermore, from these observations and analyses, insight into the nature of the A1-A12O3 (thermally grown) interface region has been obtained.&apos;&apos; The temperature dependence of the tunnel current has also been studied and, although a self-consistent set of tunneling parameters can be chosen to describe these data at low voltages (i.e., <0.5 v), the tunneling parameters are different from those obtained from higher voltage (i.e., of the order of 1 to 5 v) measurements." We have measured the effect of temperature and voltage upon the tunnel current at higher applied voltages and find that the theory is inadequate to describe all of the effects reported here. A discussion of the origin of this inadequacy is presented following a description of the samples used for these experiments, and the experimental results. SAMPLE PREPARATION Metal-insulator-metal structures were fabricated in the following way. A 99.999 pct A1 charge was used to deposit, in vacuo, thirty films, 2000Å thick, onto a 1 by 2 in. glass substrate (7059 Corning glass). Prior to deposition the substrate was glow-discharged for final cleanup and then baked at 200°C for 2 hr at a pressure of 5 x 10-7 torr. The pressure during deposition of the metal films was 2 X 10-6 torr and the deposition rate was 50 to 100Å per

Jan 1, 1965

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Jan 1, 1980

By A. T. Miesch, L. B. Riley

An error occurred in the preparation of Fig. 3, p. 249, of Basic Statistical Measures Used in Geo-chemical Investigations of Colorado Plateau Uranium Deposits. This figure shows the relation of the arithmetic mean: geometric mean ratio to the geometric deviation. Curves for the cases where n, the number of samples, is 100, 10, and 5 are too high with respect to the ordinate. The error is negligible at low geometric deviations, but becomes increasingly greater wi,th higher values of geometric deviation. Arithmetric mean values in Table I1 are not effected by the errors in Fig. 3. The authors will endeavor to supply copies of the revised curves on request; write to: A. T. Miesch, Geologist, Branch of Radioactive Materials, U.S. Geological Survey, Bldg. 25, Federal Center, Denver 25, Colo.

Jan 1, 1962

By Aziza A. Yousef, Suzan S. Ibrahim, Mahmoud A. Arafa, Mohamed A. Abdel Khalek

Due to the shortage of fresh water in the Middle East, seawater has been used as an alternative in flotation beneficiation. The flotation process requires about 7 m3 of water/mt ore. This article aims to study the effect of seawater cations and anions on the flotation. Natural pure francolite, calcite, dolomite and quartz were characterized by chemical, thermal and x-ray diffraction analyses, surface area, solubility and zeta potential. Synthetic seawater was prepared with the major chemical composition similar to natural seawater as follow; 2.45% NaCl, 0.52% MgCl2, 0.41% Na2SO4, 0.116% CaCl2 and 0.07% KCl. Also, natural seawater was used in application. The point zero of charge was estimated at pH 6.5, 7.8, 9.2 and 2.2 for francolite, calcite, dolomite and quartz, respectively. Calcium ions were released from the three minerals with Mg2+ and P2O5 3– released from dolomite and phosphate, respectively. The adsorption of collector, zeta-potential and floatability of pure minerals were studied. The effect of individual cations and anions predominant in seawater are studied on individual mineral or group. The troublesome Ca2+ and Mg2+ ions should be controlled by soda ash addition. Sodium silicate improved the selectivity of mineral mixtures and natural ore. At optimum conditions the calcareous phosphate ore yielded a concentrate of 34% P2O5, at 83% recovery with 0.61% MgO, from an ore assaying 25.3% P2O5 and 9.4% MgO. To minimize the Clcontent, fresh water of about 0.5 m3 /t was used and the Cl- decreased to about 0.09 %

Jan 1, 2003

By Joelma Krugel Brites

Com a perspectiva do uso de aços API em ambientes sour service, o controle de inclusões e precipitados é essencial para bom desempenho. A precipitação de carbonetos e nitretos de Nb e Ti, assim como a formação do MnS foram analisados criticamente em aços de alta resistência e baixa liga – HSLA- com Mn entre 0,3 e 1,6%, Nb 0,02-0,1%, S 0,001-0,005% e Ti 0-0,02% em peso. Os valores da temperatura de precipitação do MnS, Nb(C,N) e Ti(C,N) foram obtidos por meio do software ThermoCalc™. A partir desses resultados, possíveis tendências da precipitação foram discutidas e relacionadas com a temperatura de não-recristalização, traçando um comparativo entre temperaturas de processo e precipitação. Três aços produzidos com a composição estudada atenderam os requisitos mecânicos de tração da norma API 5L X65M.

Oct 30, 2017

Some Things We Don&apos;t Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

Some Things We Don&apos;t Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

By Catharina Rebucci Ribeiro Orsoli

Com o crescimento do mercado tecnológico, os modelos de aparelhos eletrônicos sofreram adaptações, principalmente em relação aos tamanhos os quais se tornaram: menores, mais leves e com mais rapidez operacional. Alguns resíduos de equipamentos eletroeletrônicos contem terras raras (TRs) em sua composição. Os elementos que compõem as terras raras de REEEs são compostas por 17 elementos (grupo lantanídios, escândio e ítrio) que conseguem suprir estas novas necessidades do mercado. Este trabalho tem como finalidade a reciclagem destas TRs entendendo primeiramente a individualidade de cada tipo de bateria, já que suas destinações pós-uso não possuem rotas definidas de tratamento. Para a caracterização foram coletadas cerca de 4,5 kg de pilhas e baterias obtidas de uma entidade recicladora da USP. Os materiais foram divididos em 12 grupos com semelhanças especificas como: marca e local de produção. Em seguida as pilhas e baterias passaram pelo britador de mandíbulas, e após 3 dias de secagem à temperatura ambiente, os materiais passaram por um moinho de facas utilizando grelhas de 3 mm. O material moído e dividido em frações de 100 g, sendo uma fração para digestão ácida, uma para perda ao fogo e o restante direcionado para a rota hidrometalúrgica para extração, identificação e quantificação das TRs presentes em pilhas e baterias de Níquel Metal Hidreto, visando à obtenção seletiva das TRs.

Aug 8, 2018

By M. Pakala, Z. Fan, Ray Y. Lin

Deposition of hard chromium coatings using electrodeposition is accompanied by emission of hexavalent chromium mists which is a carcinogenic. Hence alternative chromium deposition technologies are being investigated. Sputter deposition is a strong candidate to economically deposit hard chromium coatings in an environmentally friendly way. Chromium coatings of 2-3 µ m thickness were deposited on plain carbon steel coupons using RF magnetron sputter deposition. Depositions were carried out with 0 to 22 vol% nitrogen in the plasma. Structure of the coatings was studied using x-ray diffraction analysis With increasing nitrogen contents, formation of the two nitride phases was observed. The pure chromium phase was detected in coatings with up to 7% nitrogen in the sputtering gas. The solid solution of nitrogen in the pure Cr phase coating was identified by shifts of Cr x-ray diffraction peaks to higher d-spacing. The microhardness of the coatings deposited at a substrate temperature of 200°C showed an increase in hardness with increasing nitrogen content from 600 kgf/mm2 (5.9 GPa) at 0% nitrogen to I250 kgf/mm2 (I2.25 GPa) at 9.5 % nitrogen and a subsequent decrease in hardness to I 100 kgf/mm2 (11 GPa) beyond 9.5 % nitrogen in the sputtering gas. This corresponds to the formation of the hard Cr2N phase, at 9.5 % nitrogen, and CrN phase, at I5.7 % nitrogen. The reported bulk hardness values of Cr2N and CrN are I600 kgf/mm2 (I5.7 GPa) and I 100 kgf/mm2 (11 GPa) respectively. For pure Cr phase coatings, there is a slight increase in hardness for coatings deposited at 7. I % nitrogen from that without nitrogen in the sputtering gas. This could possibly result from the solid solution strengthening of the Cr lattice by nitrogen. For films deposited at 200°C, phases of the deposited films seem to be the overwhelming factor in controlling the microhardness.

Jan 1, 1998