Spatial Organization of a Metal–Polymer Nanocomposite Obtained by the Radiation-Induced Reduction of Copper Ions in the Poly(Allylamine)–Poly(Acrylic Acid)–Cu2+ System

doi:10.1016/j.mencom.2012.06.014

Mendeleev Communications

Volume 22, Issue 4, July–August 2012, Pages 211-212

https://doi.org/10.1016/j.mencom.2012.06.014 Get rights and content

The X-ray-induced reduction of Cu²⁺ ions in aqueous–alcoholic suspensions containing poly(allylamine) and poly(acrylic acid) leads to a specific microheterogeneous structure with microdomains (100–200 nm) enriched by small copper nanoparticles (2 to 4 nm), which are dispersed in a continuous matrix.

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In recent years, the progress in the synthesis of metal–polymer nanostructures by different methods was associated with the use of coatings and films of IPECs (Pergushov et al., 2014; Shi et al., 2004; Demchenko et al., 2017a, 2017b). Different combinations of polyanions and polycations were used for the preparation of films and soluble metal-polymer hybrids: poly(acrylic acid) - polyethyleneimine (PAA-PEI) (Dai and Bruening, 2002; Feldman et al., 2013; Klimov et al., 2018; Lei et al., 2008; Zezin et al., 2010); PAA-polyallylamin (Bakar et al., 2012, 2014); pectin and PEI (; Demchenko and Shtompel’, 2014) PAA - poly(allylaminehydrochloride) (PAH) (Bruening et al., 2008; Wang et al., 2002, 2003). The advantages of synthesis of metal nanoparticles in multilayer polyanion-polycation systems (IPECs) and the development of this method were discussed previously (Shi et al., 2004).
The radiation-chemical synthesis of metal nanoparticles embedded into polymer matrices is an effective tool for preparation of the composite materials with very useful functional properties. This paper presents a review of an original approach to a single-step production of such materials via the radiation-induced reduction of the interpolyelectrolyte complex (IPEC) films containing metal ions under heterogeneous conditions, including the most recent results, and analysis of the prospects of this approach and its implications. First, the properties of IPECs as precursors for nanocomposites are briefly considered. Particular impact is given to the mechanistic aspects and principles of control of the nanoparticle formation and assembling at different stages. A common procedure of the radiation-chemical synthesis of metal polymer nanocomposites in the IPEC matrices implies irradiation of swollen films in an aqueous – organic environment. The kinetics of ion reduction and formation of nanoparticles was monitored by EPR and optical spectroscopy, whereas the obtained nanocomposites were characterized by TEM and diffraction methods. Using IPEC matrices allows us to reveal different stages of formation of metal nanostructures over a wide range of absorbed doses. Furthermore, it is possible to manipulate the processes of nucleation and growth of nanoparticles using both physical and chemical factors. Different kinds of radiation (e-beams, γ- and X-rays) were used in the experiments. It was shown that the penetration depth, dose rate and total absorbed dose had strong effect on the effect on nanoparticle size and their spatial distribution. The most striking feature were found for the processes induced by X-ray radiation. Detailed studies of this particular case revealed a very interesting effect described as radiation-chemical contrast, which is manifested by local intensification of the radiation-induced processes in the vicinity of existing nanoparticles. In addition to metal nanoparticles of different transition and noble metals, it was possible to obtain the bimetallic nanostructures within the IPEC matrix. Such nanocomposites may be potentially used as optical and magnetic materials, sensors, bactericide and fungicide products. The possibility of variation of nanoparticle size and specific properties of the IPEC films is crucially important for particular applications.
Radiation-induced preparation of metal nanostructures in coatings of interpolyelectrolyte complexes
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Citation Excerpt :
The use of chemical approaches for the reduction of metal ions in such systems resulting in formation of the nanoparticles of silver and noble metals was reported previously (Dai and Bruening, 2002; Macanás et al., 2010; Dotzauer et al., 2009). Recently silver or copper nanoparticles and bimetallic nanostructures were synthesized in solutions and films of interpolyelectolyte and interpolymer complexes irradiated in water-alcohol media using accelerated electrons, γ- or X-ray irradiation (Bakar et al., 2012, 2014; Klimov et al., 2018; Feldman et al., 2013; Zezin et al., 2011a) It should be noted that the metal ions are strong absorbers for X-ray photons in the energy range up to several tens of keV, which results in significant increase in the absorbed dose rate for metal polymer complexes. The intensification of nanoparticle assembling in the systems with high content metal ions makes it possible to use X-ray irradiation for effective production of the metal-polymer film nanocomposites (Feldman et al., 2013; Zezin et al., 2009, 2011b).
Copper, silver and gold nanoparticles were obtained by reduction of metal ions under X-ray irradiation of “layer-by-layer” (LbL) coatings in a water-alcohol medium. The precursors for metal polymer composites (metallopolymer complexes) were prepared by sorption of metal ions in polyethyleneimine - poly (styrenesulfonic acid) and polyethyleneimine - poly (acrylic acid) coatings deposited on cotton fibers. EPR spectroscopy was use to characterize the complexation of metal ions in coatings with different chemical structure and variable number of polyanion-polycation layers. The effect of coating structure and thickness on the size and stability of nanoparticles was studied using TEM and microdiffraction measurements. Antibacterial activity was found for composites containing silver nanoparticles.
Nanocomposites based on interpolyelectrolyte complex and Cu/Cu<inf>2</inf>O core-shell nanoparticles: Structure, thermomechanical and electric properties
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Copper’s nanoparticles possess an interesting optical properties, high catalytic, antibacterial and fungicide activities and this urges an interest for design and preparing a metallo-polymer and hybrid composites, having controllable structure and particles of nano-size level. In the last decade, researches dealing with elaboration of such hybrid materials [18–21], including synthesis of Cu-nanoparticles directly in a polymers films [11,22,23], are intensively developed. In particular, in the publications [8,23,24] structure and physico-mechanical characteristics of nanocomposites based on interpolyelectrolyte complex (IPEC), like polyacrylic acid–polyethyleneimine and Cu2O nanoparticles were studied.
The morphology, structural, thermomechanical and electric properties of nanocomposites prepared from interpolyelectrolyte–metal complex being formed involving anionic polyelectrolyte – pectin, CuSO₄ and cationic polyelectrolyte – polyethyleneimine have been investigated using the methods of wide-angle X-ray scattering, transmission electronic microscopy, thermomechanical analysis and dielectric spectroscopy. Such type of nanocomposites with Cu/Cu₂O core–shell nanoparticles incorporated into polymer matrix is obtained due to the chemical reduction of Cu²⁺ cations by NaBH₄ in the interpolyelectrolyte complex, and appearance of the copper’s metallic phase is observed in full extent while BH₄⁻:Cu²⁺ molar ratio is equal to 6.0. Applying thermomechanical analysis and dielectric spectroscopy, it was observed that transformation of interpolyelectrolyte–metal complexes into nanocomposites results in decreasing of their glass-transition temperature and increasing of the electric conductivity.
Controlling the size and distribution of copper nanoparticles in double and triple polymer metal complexes by X-ray irradiation
2014, Radiation Physics and Chemistry
Copper nanoparticles were synthesized in double and triple polymer/metal ion complexes of poly(allylamine) (PAlAm)-copper(II), poly(allylamine)-poly(acrylic acid) (PAA)-copper(II) in aqueous solution in the presence of alcohol by irradiation with X-rays. Structural characterization of synthesized PAlAm-Cu, and PAlAm-PAA-Cu nanocomposites was carried out by transmission electron microscopy (TEM) and the radiation-induced reduction was monitored by UV–vis spectroscopy. The electron microscopy studies have demonstrated that the size of Cu nanoclusters is 2–4 nm in triple polymer metal complexes, whereas the double system yields copper nanoparticles with a very wide size distribution. The metal nature of nanoparticles was confirmed by microdiffraction measurements.
A one-pot radiation-chemical synthesis of metal-polymeric nanohybrides in solutions of vinyltriazole containing gold ions
2019, Mendeleev Communications
Preparation of Biocidal Nanocomposites in X-ray Irradiated Interpolyelectolyte Complexes of Polyacrylic Acid and Polyethylenimine with Ag-Ions
2022, Polymers

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Spatial Organization of a Metal–Polymer Nanocomposite Obtained by the Radiation-Induced Reduction of Copper Ions in the Poly(Allylamine)–Poly(Acrylic Acid)–Cu2+ System

Nanostruct. Mater.

Nucl. Instrum. Meth. Phys. Res. B

Adv. Colloid Interface Sci.

Nature

Izv. Akad. Nauk, Ser. Khim.

J. Phys. Chem. B

Spatial Organization of a Metal–Polymer Nanocomposite Obtained by the Radiation-Induced Reduction of Copper Ions in the Poly(Allylamine)–Poly(Acrylic Acid)–Cu²⁺ System