Synthesis and characterization of novel functional composite matrix filled with metallopolymer nanoparticles with enhanced mechanical property and higher thermal stability.

Joint research project

Project leaders: Mauro Zarrelli, Anatolii Pomogailo
Agreement: RUSSIA - RAS old - Russian Academy of Sciences old
Call: CNR/RAS 2011-2013
Department: Molecular Design
Thematic area: Chemical sciences and materials technology
Status of the project: New

Research proposal

The nowadays trend of material research is to develop multifunctional materials opportunely design for the specific service life. Epoxy resins are very important class of thermosetting polymers that often exhibit high tensile strength and modulus, excellent chemical and corrosion resistance and good dimensional stability. Hence, they are widely used in structural adhesives, surface coatings, composite matrix for bearing and no bearing applications. The major drawback of epoxy resins in the cured state is that they are extremely brittle materials and characterised by poor thermal stability. As the result they have limited utility in applications of materials with high impact and fracture strengths and more in general they may not be used in element where high temperature is expected or in hazard fire scenario. One of the most common toughening methods involves adding soluble rubber modifiers that phase separately into micron-sized particles during cure. Another method for improving toughness has been the addition of inorganic inclusions. It is reported three-fold increases in fracture toughness of an amine-cured epoxy with approximately 25-μm glass particles [1]. Recent works [2-3] has shown a synergistic toughening effect by adding rubber and inorganic nanosilica to a diglycidyl ether of bisphenol-F epoxy cured with diethyltoluene diamine. The widely used way to enhance the strength of epoxy binders is the introduction of plasticizers and antiplacticizers [4]. However, as drawback, the polymer matrix heat resistance considerably decreases. More recently, material engineers have studied extensively the effect of nanotubes and silicate nanoparticles to enhance the fracture toughness, mechanical modulus and the thermal stability of composite matrix. Results in both cases, are very promising but technological problem such as good dispersion and scale-up processes has reduced the expectations [5]. To enhance the thermal stability of composite matrix controlling also the processing parameters and the final composite mechanical property, micro fillers such zinc oxide or ammonium polyphosphate have been used. Results show that the fire propriety of the composite systems may be increased and also the processing conditions may not be changed considerably by balancing the filler content [6-7]. A novel approach to enhance the mechanical and thermal behavior of composite material may be exploit by elaborating effective approaches for modification of polymer matrix by synthesis and polymerization of metal containing monomers. This novel class of material knows as metallopolymer state its potentiality also for future scale-up development of thermally and mechanically enhanced composite matrix. An organic phase can capture metal-containing particles into a `trap' of a peculiar kind, into an oxopolymeric network or a polymeric unit with appropriate parameters. Silicon, aluminium, titanium, zirconium, vanadium and molybdenum oxides, glasses, clays, layered silicates and zeolites, metal phosphates and chalco- genides, iron oxychloride and graphite are used as inorganic precursors. Not only carbon-chain but also organoelement polymers are used as a polymeric component. In the resulting nanocomposite materials, distances between networks and layers formed by polymeric and inorganic ingredients and sizes of particles formed, including metal-containing particles, are nanometric. Generally, hybrid nanocomposites exhibit a synergism of the properties of the initial components. These compounds are characterised by an enhanced mechanical strength and thermal stability and provide optimum heat transfer. In metallomatrix composites, the strength and hardness of soft metals, for example, of aluminium, are enhanced. These materials possess good thermochemical, rheological, electrical and optical properties. [8-11].
The Russian team have dealt with metallopolymers and nanocomposites, polymer-polymer composites including ones formed in situ. In last years, ynthesis and polymerization of metal-containing monomers was developed for one-stage obtaining structural-homogeneous macrocomplexes. The new methods of synthesis and polymerization (frontal and thermal polymerization in the solid phase etc.) of these monomers were elaborated. Also the methods for obtaining metal-containing polymers of condensation type with metal atoms in the backbone were elaborated. Using the metal-containing polymers the precursors of new types for high temperature superconducting ceramics, polymer ferromagnetic materials, the ingredients of polymer-polymer composites were obtained. The new approaches for the formation of metal nanosized particles in polymer matrices including the formation of such nanocomposites in situ were developed. The special attention is paid to study of mechanism of simultaneous formation of nanosized metal particles and polymer matrix during polymerization of metal-containing monomers as well as to synthesis of hybride polymer-inorganic materials.
[i]) Lee, J. et al. Polymer 2000, 41, 8375–8385
[ii]) AJ. Kinloch J. of Adhesion 2003, 79, 867–873; Sprenger, S.;
[iii]) AJ. Kinloch JEC Composites 2005, 9, 73–76; Sprenger, S.;
[iv]) Khozin V.G. Reinforcement of epoxy polymers. Kazan. Dom pechati. 2004.
[v] ) A. Martone, C. Formicola, M. Giordano, M. Zarrelli Composite Science and Technology 70 (2010) 1154–1160
[vi]) C. Formicola, A. De Fenzo, M. Zarrelli, A. Frache , M. Giordano, G. Camino eXPRESS Polymer Letters Vol.3, No.6 (2009) 376–384
[vii]) C. Formicola, A De Fenzo, M. Zarrelli, M. Giordano, V. Antonucci ID. PI-10-0104.RI
[viii]) AD. Pomogailo et al. Monomeric and Polymeric Metal Carboxylates. Moscow, Fizmatlit, 2009
[ix]) AD. Pomogailo et al. Preparation of Hafnium-Containing Nanocomposites Springer, 2008, p. 241-267.
[x]) A.D. Pomogailo et al. Russ. Chem. J. , 2009, V. 53, P.140-151
[xi]) G.I. Dzhardimalieva et al. Reactivity of Metal-containing monomers. 66. Ser. Khim., 2009, N10, P.2007-2013.

Research goals

The main objective of the proposed collaboration between the laboratory of metallopolymers of RAS and the IMCB is to develop a novel class of material based on metallopolymer nanoparticles which could be used as tailored filler for advanced composite materials. A novel functional hybrid matrix based on epoxy polymer modified with metallopolymers with aim to enhance physical-mechanical, thermal stability and adhesion properties will be developed and characterized along with their fiber reinforced composite. The main stages of the project will be:
a) elaboration of methods of synthesis of metal-containing monomers based on glycidic alcohols and unsaturated dicarboxylic acids, characterization of their composition and structure using elemental analysis, IR-, NMR spectr.;
b) synthesis and characterization of modified epoxide composites with metallopolymers in situ;
c) synthesis and characterization of metal-containing nanoparticles stabilized with polymer matrix using polymer-assisted synthesis via thermal transformations of metal-containing monomers. The characterization of phase composition of nanocomposites obtained, the size of nanoparticles and their distribution on the size and in polymer matrix will be performed;
d) optimization of nanoparticles dispersion of metallopolymer in epoxy matrix;
e) nanocomposite characterization (morphology, mechanical rheological, electrical and degradation);
f) preparation and characterization of composite materials based on carbon- and glass fibers;

Last update: 26/04/2024