Massimo Messori

Facile preparation of superhydrophobic coatings by sol–gel processes

Different organic/inorganic compositions and deposition methods were used to prepare superhydrophobic surfaces using metal alkoxides and the sol-gel process. Both surface roughness and composition had to be adjusted in order to obtain very high contact angles and low contact angle hysteresis as a necessary requirement for superhydrophobicity. Multilayer samples with a fluorinated organic-inorganic top layer showed water contact angles of about 157 degrees with low hysteresis (2 degrees ). Water drops rolled easily off their surface at a tilt angle as low as 4 degrees .

Flame retarding poly(methyl methacrylate) with nanostructured organic–inorganic hybrids coatings

Abstract Organic–inorganic hybrid materials were prepared starting from tetraethoxysilane and α- or α,ω-triethoxysilane terminated poly(e-caprolactone) (PCL–Si) using the sol–gel process. In all cases the formation of nanocomposites with a high level of interpenetration between organic and inorganic phases was noted. Poly(methyl methacrylate) slabs were dip-coated with PCL–Si/silica hybrids and a very strong increase of the flame resistance (also after UV irradiation) was noted for all coating compositions without marked differences with respect to hybrid compositions. This behavior was attributed to a preferential segregation of silica onto the outer surface, as evidenced by XPS analysis.

Porous scaffolds of polycaprolactone reinforced with in situ generated hydroxyapatite for bone tissue engineering.

Polycaprolactone/hydroxyapatite (PCL/HA) composites were prepared by in situ generation of HA in the polymer solution starting from the precursors calcium nitrate tetrahydrate and ammonium dihydrogen phosphate via sol–gel process. Highly interconnected porosity was achieved by means of the salt-leaching technique using a mixture of sodium chloride and sodium bicarbonate as porogens. Structure and morphology of the PCL/HA composites were investigated by scanning electron microscopy, and mechanical properties were determined by means of tensile and compression tests. The possibility to employ the developed composites as scaffolds for bone tissue regeneration was assessed by cytotoxicity test of the PCL/HA composites extracts and cell adhesion and proliferation in vitro studies.

Unsaturated polyester resins modified with poly(ε-caprolactone)–perfluoropolyethers block copolymers

Poly(e-caprolactone)–perfluoropolyether–poly(e-caprolactone) block copolymers (TXCL) synthesised from Fomblin Z-DOL TX (TX) have been mixed with conventional unsaturated polyester resins (UPR) to prepare fluorine modified UPR (FUPR). A preliminary investigation on the compatibility of uncured FUPR systems has shown that the presence of PCL blocks leads to an enhancement of compatibility with respect to pure perfluoropolyether macromers. The compatibility tends to decrease by increasing the TXCL concentration in the mixture depending on both molecular weight and TX/PCL ratio. Also the morphology of FUPR after curing was strongly affected by the rate of curing and by a critical balancing of TX/PCL ratio and molecular weight of TXCL copolymers. Both transparent and opaque FUPR were obtained for the same composition at different curing rates; high curing rates (i.e. high concentration of initiator/activator) favoured the formation of transparent FUPR through a kinetic control of phase separation. Scanning electron microscopy (SEM) analysis was in good agreement with the macroscopic results obtained by visual inspection. XPS analysis showed a very strong surface enrichment in fluorinated segments, which increases by increasing the TX/PCL ratio. Mechanical tests showed a slight plasticization effect (compared to UPR control) together with a very strong improvement in the absorbed energy at break EB showing the best toughening effect for TXCL with intermediate TX/PCL ratio. Finally, a minimisation of the water diffusion coefficient value (five times lower than UPR control) was noted for UPR modified with TXCL having intermediate PCL segment length.

Poly(ϵ-caprolactone)-poly(fluoroalkylene oxide)-poly(ϵ-caprolactone) block copolymers. 2. Thermal and surface properties

Abstract The thermal and the surface properties of PCL–PFPE–PCL block copolymers having different PCL and PFPE block lengths were investigated by DSC, contact angles and XPS measurements. DSC analysis reveals for all the copolymers the presence of different amorphous phases; the phase located at low temperature was attributed to the fluorinated moiety. Tm values also demonstrated that PCL crystallizes from a pure phase. XPS measurements showed a strong surface enrichment in PFPE with respect to the bulk. Contact angle values showed a hydrophobic character of the film surface even if the trend was found not depending on the fluorine concentration as detected by XPS: this behavior may be explained by the presence of very flexible blocks, providing a highly dynamic surface. These structures can be potentially used as additives for the formation of polymers having ‘smart surfaces’ with selective adhesive properties.

On specific factors affecting the crystallization of PET: the role of carboxyl terminal groups and residual catalysts on the crystallization rate

Abstract The non-isothermal crystallization rate of poly(ethylene terephthalate) (PET) has been studied in differential scanning calorimetry experiments, by cooling from the molten state of samples of various molecular weights, prepared using various catalysts (mainly Ti(O- n -Bu) 4 ). The crystallization temperature, T cc , was obviously influenced by the molecular weight, but also by the carboxyl group content, by the type of residual catalyst, by dissolution-reprecipitation treatments and by re-melting phenomena. The observed effects were interpreted assuming that interactions of terminal groups of the PET chains (mutual or with residual catalyst) led to an apparent increase in molecular weight, which in turn determined a decrease in the chain mobility and was responsible for a decrease in the rate of crystallization. Thus, a higher concentration of carboxyl terminal groups as well as interactions of PET terminal groups with the catalyst decreased T cc . Any factor which was able to destroy these interactions (treatments of dissolution-reprecipitation, phosphorous derivatives, aging) led to an increase of the overall crystallization rate.

New catalysts for poly(butylene terephthalate) synthesis: 1. Titanium–lanthanides and titanium–hafnium systems

Abstract A complete study of the catalytic activity of lanthanide- and hafnium acetylacetonate catalysts in PBT synthesis was conducted in order to investigate any improvement in the process and/or in the properties of the final polymer with respect to the industrially used titanium tetrabutoxide (TBT) catalyst. Small scale polymerization and subsequent scale up in higher capacity reactors showed that TBT-Hf(acac) 4 and TBT-La(acac) 3 mixed catalysts were more active with respect to TBT as single catalyst. Decreases in polymerization time and THF formation were also observed, which in turn can improve the productivity of the whole process. Furthermore, for similar values of molecular weight, a lower melt viscosity (and thus better processability and crystallizability) was obtained by using mixed catalysts, presumably due to weaker interactions of the polymer terminal groups to lanthanum and hafnium metals with respect to titanium.

Shape-memory polymer networks from sol–gel cross-linked alkoxysilane-terminated poly(ε-caprolactone)

A novel type of covalently cross-linked semi-crystalline polymer with shape-memory and biocompatibility properties was prepared from alkoxysilane-terminated poly(ε-caprolactone) (PCL) by sol–gel process that allowed the generation of silica-like cross-linking points. A fine tuning of the cross-linking density and thermal properties (melting temperature) of the materials was obtained by controlling the molecular weight of the PCL precursor (and thus the molecular structure of the resulting network) and the curing conditions. The shape-memory behaviour was investigated with bending tests. Recovery times of less than one second were observed in water depending on the temperature, and a linear correlation of the recovery time with cross-linking density and molecular weight of PCL network precursor was observed.

Improving Epoxy Adhesives with Zirconia Nanoparticles

Zirconia nanoparticles were synthesized by a sol–gel route and dispersed into an epoxy base for structural adhesives. Nanoparticles were used as-synthesized or after calcination. Moreover, the effect of silane functionalization was also investigated. According to preliminary tensile mechanical tests on bulk nanocomposite samples, calcined and untreated zirconia nanoparticles were selected for the preparation of adhesives with various filler contents. The glass transition temperature increased up to a filler content of 1 vol% and then decreased, probably due to the concurrent and contrasting effects of chain blocking and reduction of the crosslinking degree. Also tensile modulus, stress at break and fracture toughness of bulk adhesives samples were positively affected by the presence of an optimal amount of zirconia nanoparticles. Mechanical tests on single lap aluminium bonded joints indicated that zirconia nanoparticles led to relevant enhancements of the shear strength of the joints. In particular, the shear strength increased by about 60% for an optimal filler content of 1 vol%, and an adhesive failure mechanism was evidenced for all the tested specimens. Concurrently, a significant decrease of the equilibrium contact angle with water was observed for adhesives containing zirconia nanoparticles. It can therefore be concluded that the addition of zirconia nanoparticles can effectively improve epoxy adhesives, both by increasing their mechanical properties and by enhancing the interfacial wettability with an aluminium substrate.

Synthesis and characterisation of silica hybrids based on poly(ε-caprolactone-b-perfluoropolyether-b-ε-caprolactone)

Abstract Poly(e-caprolactone-b-perfluoropolyether-b-e-caprolactone) (PCL–PFPE–PCL) triblock copolymers having hydroxy end groups were readily functionalised with triethoxysilane end groups by reactions with 3-isocyanatopropyltriethoxysilane. Organic–inorganic hybrids were prepared by using the sol–gel process in the presence of tetraethoxysilane and hydroxy or triethoxysilane terminated PCL–PFPE–PCL. Fully transparent hybrid materials with high content of organic matter were obtained only in the case of alkoxysilane functionalised copolymers. For such systems the PCL–PFPE–PCL copolymer was so intimately mixed with the inorganic network to prevent crystallisation of the PCL segments. The progress of the sol–gel reaction was limited by the early vetrification of the reactive system, while the interpenetration of the organic phase was enhanced by curing the samples at 100 °C.