Giovanni Moggi

Synthesis and microstructural characterization of low-molar-mass poly(vinylidene fluoride)

Abstract The kinetic features of vinylidene fluoride (VDF) radical polymerization in solution, initiated by bis(4-butylcyclohexyl)peroxydicarbonate, have been investigated in three different solvents (acetone, ethyl acetate and methyl acetate) under homogeneous conditions. Many significant deviations of the dependence of the polymerization rate on the ‘ideal’ 1.0 and 0.5 exponent values of monomer and initiator concentrations, respectively, are indicative of anomalous kinetic behaviours linked to concurrent reactions, which are operative during such polymerization. The complexity of the kinetic behaviour prevents, inter alia , the correct evaluation of chain transfer constants to the solvents from kinetic data. 19 F nuclear magnetic resonance spectroscopy has been used in order to get full microstructural characterization of the low-molar-mass poly(vinylidene fluoride) (PVDF) synthesized under the above conditions. Both chain transfer constants to the solvent and extent of chain inversions in PVDF have been evaluated by this technique.

Fluoroelastomers-dependence of relaxation phenomena on composition

Abstract The dynamic-mechanical properties of some fluoroelastomers were determined as a function of composition at low frequency (≈ 1 Hz), by means of a free oscillation torsion pendulum, between −180°C and the softening point. Vinylidenefluoride (VDF)-hexafluoropropene (HFP) copolymers of molar composition 0–39% HFP and terpolymers of VDF and HFP with up to 30mol% tetrafluoroethylene (TFE) and a constant VDF to HFP molar ratio of 3.4 were considered. Two relaxation processes typical of the amorphous phase were found. The first, located at about −87°C, is related to local motions and the transition temperature was found to be independent of composition for copolymers, while it depends on TFE molar content for terpolymers. The second is related to the glass transition and the transition temperature depends on the composition. However, for semicrystalline copolymers the double glass transition phenomenon was observed. When crystallinity goes to zero at about 20 mol% HFP, only one transition is observed. It was also found that ordered structures can take place for terpolymers when TFE molar concentration exceeds 20%. The crystal disorder transition of pure PVDF (75°C) is observed also for low HFP concentrations but the transition temperature is strongly reduced. Analogies between the VDF-HFP and E-P systems are also discussed.

FTIR-microspectroscopy and DSC studies of poly(vinylidene fluoride)

Poly(vinylidene fluoride) (PVDF) samples, obtained by casting from tetrahydrofuran solutions and submitted to various thermal treatments, have been examined by Fourier transform-infrared microspectroscopy (FTIR-M) and differential scanning calorimetry (DSC). This kind of analysis allowed us to examine microdomains of samples with different morphological characteristics and to obtain an indication of the polymorphism of PVDF. In some cases the simultaneous presence of two or three forms has been evidenced thanks to the comparison of FTIR-M spectra and DSC traces. Vibrational spectra of single crystalline forms can be recorded by FTIR-M on phase homogeneous microdomains.

Characterization of acrylic resins and fluoroelastomer blends as potential materials in stone protection

Films of blends of Paraloid® B72 (copolymer of ethyl methacrylate and methyl acrylate) and Tecnoflon NM® (copolymer of vinylidene fluoride and hexafluoropropene) with different compositions were investigated by means of FT-IR spectroscopy and FT-IR microspectroscopy before and after UV and thermal treatments. Preliminary results of DSC measurements are also reported. Paraloid B72 has been extensively applied as a protective agent for stone since the 1950s. More recently considerable research has also been carried out on the application of fluorinated polymers in the field of stone conservation, eg the fluoroelastomer Tecnoflon®. A high content of Tecnoflon with respect to Paraloid increases the stability of the blends when they are submitted to UV radiation and thermal treatments. A THF solution of a blend of this kind was successfully applied to a marble surface of the Saint Maria Cathedral in Lucca, Tuscany, Italy. The changes in the properties of such mixtures with different compositions can offer new possibilities in developing suitable protective materials. © 2000 Society of Chemical Industry

Influence of molecular weight on the crystallization of poly(vinylidene fluoride)

AbstractFive samples of Poly (vinylidene fluoride) with a molecular weight from 45,000 to 260,000 were analyzed by means of FT-IR spectroscopy in order to study the influence of molecular weight

Curable compositions based on fluoroelastomers vulcanizable with peroxides

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Vulcanizable compositions of fluoroelastomers having improved characteristics of processability and of chemical stability

on the crystallization process. The spectra of films obtained from methylethylketone solutions revealed the prevalence of form II (α) in the case of lower