Materials Science and Engineering / Malzeme Bilimi ve Mühendisliği

Permanent URI for this collectionhttps://hdl.handle.net/11147/4719

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End date: 2009Publisher: search.filters.publisher.American Chemical Society

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  • Article
    Citation - WoS: 69
    In-Situ Bulk Polymerization of Dilute Particle/Mma Dispersions
    (American Chemical Society, 2007) Demir, Mustafa Muammer; Castignolles, Patrice; Akbey, Ümit; Wegner, Gerhard
    Composites of poly(methyl methacrylate) and various nanoscale inorganic particles (zinc oxide, titanium dioxide, zirconium dioxide, silicon dioxide, and aluminum nitride) were prepared by in-situ bulk polymerization using 2,2′-azobis(isobutyronitrile) as initiator. The particles of ZnO, TiO 2, and ZrO2 were surface-modified by alkylphosphonic acids to render them dispersible in the monomer. The effect of these nanoparticles on the free radical polymerization was investigated. Regardless of chemical nature and size, the particles suppress the autoacceleration which would otherwise occur in the bulk free-radical polymerization of methyl methacrylate (MMA). A degenerative chain transfer is proposed to take place between surface-adsorbed water on the particles and propagating chain radicals. This reaction competes with normal termination. Formation of vinylidene chains ends originating from disproportionation is suppressed. In consequence, thermal stability of PMMA produced in the presence of particles is improved. Aggregation of individual particles upon polymerization has been observed and presumably is due to interparticle depletion attraction, even though the particles are individually dispersed in the monomer. Formation of particle clusters is suppressed when a difunctional monomer (e.g., ethylene glycol dimethacrylate) is used as comonomer. The cross-linked medium slows down the diffusion of the particles and therefore interferes with particle aggregation via a depletion mechanism.
  • Article
    Citation - WoS: 263
    Palladium Nanoparticles by Electrospinning From Poly(acrylonitrile-Co Acid)-Pdcl2 Solutions. Relations Between Preparation Conditions, Particle Size, and Catalytic Activity
    (American Chemical Society, 2004) Demir, Mustafa Muammer; Gülgün, Mehmet A.; Menceloğlu, Yusuf Z.; Erman, Burak; Abramchuk, Sergei S.; Makhaeva, Elena E.; Khokhlov, Alexei R.; Matveeva, Valentina G.; Sulman, Mikhail G.
    Catalytic palladium (Pd) nanoparticles on electrospun copolymers of acrylonitrile and acrylic acid (PAN-AA) mats were produced via reduction of PdCl2 with hydrazine. Fiber mats were electrospun from homogeneous solutions of PAN-AA and PdCl2 in dimethylformamide (DMF). Pd cations were reduced to Pd metals when fiber mats were treated in an aqueous hydrazine solution at room temperature. Pd atoms nucleate and form small crystallites whose sizes were estimated from the peak broadening of X-ray diffraction peaks. Two to four crystallites adhere together and form agglomerates. Agglomerate sizes and fiber diameters were determined by scanning and transmission electron microscopy. Spherical Pd nanoparticles were dispersed homogeneously on the electrospun nanofibers, The effects of copolymer composition and amount of PdCl2 on particle size were investigated. Pd particle size mainly depends on the amount of acrylic acid functional groups and PdCl2 concentration in the spinning solution. Increasing acrylic acid concentration on polymer chains leads to larger Pd nanoparticles. In addition, Pd particle size becomes larger with increasing PdCl2 concentration in the spinning solution. Hence, it is possible to tune the number density and the size of metal nanoparticles. The catalytic activity of the Pd nanoparticles in electrospun mats was determined by selective hydrogenation of dehydrolinalool (3,7-dimethyloct-6-ene-l-yne-3-ol, DHL) in toluene at 90°C. Electrospun fibers with Pd particles have 4.5 times higher catalytic activity than the current PoVAl2O3 catalyst.