• Title/Summary/Keyword: disproportionation

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Effect of Ga, Nb Addition on Disproportionation Kinetics of Nd-Fe-B Alloy

  • Kwon, H.W.;Yu, J.H.
    • Journal of Magnetics
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    • v.14 no.4
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    • pp.150-154
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    • 2009
  • The effect of Ga and, Nb addition on the kinetics and mechanism of the disproportionation of a Nd-Fe-B alloy were investigated by isothermal thermopiezic analysis (TPA) using $Nd_{12.5}Fe_{(81.1-(x+y))}B_{6.4}Ga_xNb_y$ (x=0 and 0.3, y= 0 and 0.2) alloys. The addition of Ga and Nb retarded the disproportionation kinetics of the Nd-Fe-B alloy significantly, and increased the activation energy of the disproportionation reaction. The disproportionation kinetics of the $Nd_{12.5}Fe_{(81.1-(x+y))}B_{6.4}Ga_xNb_y$ alloys measured under an initial hydrogen pressure of 0.02 MPa were fitted to a parabolic rate law. This suggested that during the disproportionation of $Nd_{12.5}Fe_{(81.1-(x+y))}B_{6.4}Ga_xNb_y$ alloys with an initial hydrogen pressure of 0.02 MPa, a continuous disproportionation product is formed and the overall reaction rate is limited by the diffusion of hydrogen atoms (or ions).

Pressure-Temperature Diagram of Critical Condition for Disproportionation of Nd-Fe-B Alloy in Hydrogen

  • Kwon, H.W.;Kim, D.H.;Yu, J.H.
    • Journal of Magnetics
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    • v.15 no.4
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    • pp.155-158
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    • 2010
  • The HDDR (hydrogenation, disproportionation, desorption, and recombination) process can be used as an effective way of converting a no coercivity Nd-Fe-B ingot material, with a coarse $Nd_2Fe_{14}B$ grain structure, to a highly coercive one with a fine grain structure. Careful control of the HDDR process can lead to an anisotropic powder with good $Nd_2Fe_{14}B$ grain texture; the most critical step for inducing texture is disproportionation. The critical conditions (hydrogen pressure and temperature) for the disproportionation reaction of fully hydrogenated $Nd_{12.5}Fe_{81.1-(x+y)}B_{6.4}Ga_xNb_y$ (x = 0 or 0.3, y = 0 or 0.2) alloys, in different atmospheres of pure hydrogen and a mixed gas of hydrogen and argon, was investigated with TPA (thermopiezic analyser). From this, the hydrogen pressure-temperature diagram showing the critical conditions was established. The critical disproportionation temperature of the fully hydrogenated $Nd_{12.5}Fe_{81.1-(x+y)}B_{6.4}Ga_xNb_y$ alloys was slightly increased as the hydrogen pressure decreased in both pure hydrogen and mixed gas. The critical disproportionation temperature of the hydrogenated alloys was higher in the mixed gas than in pure hydrogen. Addition of Ga and Nb increased the critical disproportionation temperature of the fully hydrogenated Nd-Fe-B alloys.

Acarbose Effect for Dexran Synthesis, Acceptor and Disproportionation Reactions of Leuconostoc mesenteroides B-512FMCM Dextransucrase

  • Kim, Do-Man;Park, Kwan-Hwa;Robyt, John F.
    • Journal of Microbiology and Biotechnology
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    • v.8 no.3
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    • pp.287-290
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    • 1998
  • Acarbose effectively inhibited the synthesis of dextran, and the inhibition pattern was a noncompetitive type with a $K_i$ value of 1.35 mM. It also inhibited the disproportionation reaction of dextransucrase with isomaltotriose and decreased the efficiency of the maltose acceptor reaction. Increased concentration of dextransucrase or maltose in reaction digests, however, decreased the degree of inhibition by acarbose.

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Improvement of Microstructural Anisotropy of Nd-Fe-B-Ga-Nb Alloy by the Control of Hydrogen Reaction (수소반응속도 제어에 의한 Nd-Fe-B-Ga-Nb 합금의 미세조직 이방화율 향상에 관한 연구)

  • Lee, S.H.;Kim, D.H.;Yu, J.H.;Lee, D.W.;Kim, B.K.
    • Journal of Powder Materials
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    • v.17 no.1
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    • pp.23-28
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    • 2010
  • HDDR treated anisotropic Nd-Fe-B powders have been widely used for the sheet motors and the sunroof motors of hybrid or electric vehicles, due to their excellent magnetic properties. Microstructural alignment of HDDR treated powders are mostly depending on the hydrogen reaction in disproportionation step, so the specific method to control hydrogenation reaction is required for improving magnetic properties. In disproportionation step, hydrogenation pressure and reaction time were controlled in the range of 0.15~1.0 atm for 15~180 min in order to control the micorstructural alignment of $Nd_2Fe_{14}B$ phase and, at the same time, to improve remanence of HDDR treated magnet powders. In this study, we could obtain a well aligned anisotropic Nd-Fe-B-Ga-Nb alloy powder having high remanence of 12 kG by reducing hydrogen pressure down to 0.3 atm in disproportionation step.

Disproportionation/Dehydrocoupling of Endocrine Disruptor, Tributyltin Hydride to Polystannanes Using Cp2TiCl2/N-Selectride (Cp' = Cp' = C5H5, Cp; Me-C5H4, Me-Cp; Me5C5, Cp*) Catalyst

  • Park, Jaeyoung;Kim, Seongsim;Lee, Beomgi;Cheong, Hyeonsook;Lee, Ki Bok;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.6 no.1
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    • pp.34-38
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    • 2013
  • Tributyltin hydride ($n-Bu_3SnH$), an endocrine disruptor, was slowly polymerized by the group 4 ${Cp^{\prime}}_2TiCl_2/N$-selectride (Cp' = $C_5H_5$, Cp; $Me-C_5H_4$, Me-Cp; $Me_5C_5$, $Cp^*$) catalyst combination to give two phases of products: one is an insoluble cross-linked solid, polystannane in 3-25% yield as minor product via disproportionation/dehydrocoupling combination process, and the other is an oil, hexabutyldistannane in 65-90% yield as major product via simple dehydrocoupling process. Disproportionation/dehydrocoupling process first produced a low-molecular-weight oligostannane possessing partial backbone Sn-H bonds which then underwent an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane. The disproportionation/dehydrocoupling of a tertiary hydrostannane mediated by early transition metallocene/inorganic hydride is quite unusual and applicable.

A Theoretical Study on the Reaction of Phosphadioxiranes and Thiadioxiranes;Disproportionation versus Epoxidation

  • Nahm, Keep-Yung
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2217-2222
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    • 2009
  • The transition structures for the epoxidations of ethylene and the disproportionations by the dioxiranes of phosphines, phosphites and sulfides were studied with density function theory methods using the Becke3LYP functional and 6-311+G(2d,p) basis set. When the dioxiranes have methyl substituents rather than hydrogen substituents, the reaction barriers ($E_{TS}$) become higher in their epoxidations of ethylene by the steric hindrance, but become lower in their disproportionations of phosphines, phosphites and sulfides, which indicates that the nature of the dioxiranes seems to be electrophilic and in their disproportionations the reaction barriers are effected both by the electrophilicity and the steric hindrance. The steric factors in the disproportionations were calculated and more bulky substituents at dioxiranes may be necessary to retard the disproportionation and to enhance the epoxidation.

APPLICATION OF DISPROPORTIONATION REACTION TO SURFACE TREATMENT

  • Oki, Takeo
    • Journal of the Korean institute of surface engineering
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    • v.29 no.5
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    • pp.478-481
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    • 1996
  • Disproportionation reaction is very important and interesting reaction to be applied to such surface treatment as metal, alloy, compound coating, a surface etching and so on. In gaseous system, the reaction of Al chloride is applied to Al and Al alloy coating, and the similar reaction of Ti chloride is also used for Ti, Ti alloy and Ti compound coating. As for aqueous system, this reaction is utilized to such metal coat as Sn etc. and metal etching such as Cu, Fe and so on. Also in molten salts system, this reaction has many application for surface treatment like metal, alloy and compound coatings for corrosion, wear, heat resistance and so forth. For instance, carbide film, nitride film, boride film, alloy film, quite new different film from the components of substrate material are coated in single and multiple component film system by the disproportionation reaction.

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Lewis Acid Degradation Characteristics of Perfluoropolyethers Derivatives (퍼프로로폴리에테르 유도체의 루이스 산 분해특성)

  • Chun, Sang-Wook;Kang, Ho-Jong
    • Polymer(Korea)
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    • v.38 no.5
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    • pp.650-655
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    • 2014
  • The degradation characteristics of perfluoropolyether (PFPE) derivatives currently being used as computer hard disk lubricants have been investigated. Especially, we considered the effects of end group on degradation behavior of PFPE derivatives. It was found that the degradation of PFPE derivatives in the presence of $Al_2O_3$ involves two degradation mechanisms such as thermal degradation and Lewis acid disproportionation by $AlF_3$ which was mainly formed by oxide-to-halide reaction between $Al_2O_3$ and the degraded PFPE. The end groups were strongly related to Lewis acid disproportionation of PFPE derivatives, and it is due to the difference of electron donating ability in the each end groups. Even if PFPE derivatives have same repeating unit in the main chain, Lewis acid disproportionation was prohibited by higher electron donating ability by the end group which caused the high electron density at the acetal group in the repeating unit.

TMA Study on Phase Evolution During Hydrogen-assisted Disproportionation of Nd-Fe-B Alloy

  • Kwon, H.W.;Yu, J.H.
    • Journal of Magnetics
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    • v.16 no.3
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    • pp.229-233
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    • 2011
  • Phase evolution during the hydrogen-assisted disproportionation of $Nd_{12.5}Fe_{80.6}B_{6.4}Ga_{0.3}Nb_{0.2}$ alloy was investigated mainly by using a magnetic balance-type thermomagnetic analyser (TMA). In order to avoid any undesirable phase change in the course of heating for TMA, a swift TMA technique with very high heating rate (around 2 min to reach $800^{\circ}C$ from room temperature) was adopted. The hydrided $Nd_{12.5}Fe_{80.6}B_{6.4}Ga_{0.3}Nb_{0.2}$ alloy started to be disproportionated in hydrogen from around $600^{\circ}C$, and the alloy after the early disproportionation (from 600 to $660^{\circ}C$) has been partially disproportionated. The partially disproportionated alloy consisted of a mixture of $NdH_x$, $Fe_3B$, ${\alpha}$-Fe, and the remaining undisproportionated $Nd_2Fe_{14}BH_x$-phase. During the subsequent heating to $800^{\circ}C$ in hydrogen, two additional phases of $Fe_{23}B_6$ and $Fe_2B$ were formed, and the material consisted of a mixture of $NdH_x$, $Fe_{23}B_6$, $Fe_3B$, $Fe_2B$, and ${\alpha}$-Fe phases. During the subsequent isothermal holding at $800^{\circ}C$ for 1 hour, the phase constitution was further changed, and one additional unknown magnetic phase was formed. Eventually, the fully disproportionated $Nd_{12.5}Fe_{80.6}B_{6.4}Ga_{0.3}Nb_{0.2}$ alloy consisted of $NdH_x$, $Fe_{23}B_6$, $Fe_3B$, $Fe_2B$, ${\alpha}$-Fe, and one additional unknown magnetic phase.

Coercivity of Hot-pressed Compacts of Nd-Fe-B-type HDDR-treated Powder

  • Abdul Matin, Md.;Kwon, Hae-Woong;Lee, Jung-Goo;Yu, Ji-Hun
    • Journal of Magnetics
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    • v.19 no.2
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    • pp.106-110
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    • 2014
  • $Nd_{12.5}Fe_{80.6}B_{6.4}Ga_{0.3}Nb_{0.2}$ HDDR-treated powder was compacted by hot-pressing using different configurations of dies and heating rates. The die configurations were especially different in terms of the evacuation system that was used in heating for hot-pressing. The coercivity in the compacts was influenced by the evacuation system of the die and heating rate. In spite of the identical hot-pressing temperature and heating rate, coercivity was radically reduced above $600^{\circ}C$ in the compacts prepared in the closed-type die compared to that in the compacts prepared in the open-type die. The coercivity in the compacts prepared in the closed-type die decreased with increasing heating rate and the value further increased when extreme high heating rate was employed. $Nd_{12.5}Fe_{80.6}B_{6.4}Ga_{0.3}Nb_{0.2}$ HDDR-treated powder contained a significant amount of residual hydrogen (approx. 1500 ppm) in the form of $Nd_2Fe_{14}BH_x$ hydride. The dramatic coercivity decrease in the compact prepared in the closed die is attributed to the disproportionation of $Nd_2Fe_{14}BH_x$ hydride. High coercivity is mainly due to the effective desorption of hydrogen or the suppression of hydrogen-related disproportionation upon hot-pressing.