Vincent Verney

Surface cross-linking of polycarbonate under irradiation at long wavelengths

Depth profiles analyses were performed on a cross section of a photoaged BPAPC substrate by measuring the glass transition temperature and the Young modulus at a microscopic scale. The aim was to define the impact of photochemical modifications induced under UV irradiation upon the physical properties of this polymer. It is well known that ageing of BPAPC begins by a direct phototransformation of the macromolecules according to the photo-Fries rearrangements. These reactions lead to an increase of the free volume and, as a consequence, to a decrease of the temperature associated with the glass transition while in the meantime, the Young modulus of the material is not modified. As ageing proceeds (longer irradiation times), oxidation of the polymer takes place. This oxidative degradation leads to the formation of a cross-linked structure on the exposed surface. This oxidative degradation is associated with an increase of the glass transition temperature and of the Young modulus, whereas in the bulk of the material ageing involves chain scissions characterised by a decreased glass transition temperature.

Porphyrin-layered double hydroxide/polymer composites as novel ecological photoactive surfaces

Nanocontainer and nanofiller aspects of layered double hydroxides (LDH) were combined to prepare porphyrin-LDH/polymer composites for photoactive coatings. The suggested properties are derived from cytotoxicity of singlet oxygen, O2(1Δg), produced by interaction of molecular oxygen with excited porphyrin molecules located within the interlayer space of ZnRAl and MgRAl LDH. Porphyrins, Pd(II)-5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin (PdTPPC) and 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) photoproducing O2(1Δg), were successfully intercalated into LDH hosts using the co-precipitation procedure and then used as fillers in two eco-friendly polymers, namely polyurethane (PU) and poly(butylene succinate) (PBS). Porphyrin-LDH/polymer composites were prepared either by the solvent cast/cross-linking technique or melt-compounding with different porphyrin-LDH filler loadings (up to 1.3 wt%). Both X-ray diffraction and transmission electron microscopy measurements indicate a good dispersion of porphyrin-LDH fillers into the polymer matrices and that the porphyrin molecules remain intercalated within LDH layers. The polymers do not block the diffusion of oxygen and the triplet states of the intercalated porphyrins in the composite films have enough long lifetimes to produce O2(1Δg) upon irradiation by visible light. The present composites allow the elaboration of photoactive surfaces with a precise control of the O2(1Δg) concentration depending on porphyrin-LDH filler loadings.

Photostability and photobactericidal properties of porphyrin-layered double hydroxide–polyurethane composite films

The photostability and photobactericidal properties of PdTPPC (Pd(ii)-5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin)-Zn2Al/PU (polyurethane) composite films have been studied in order to investigate their applicability as new photodynamic surfaces. These films comprise a PdTPPC porphyrin photosensitizer intercalated between the lamella of Zn2Al layered double hydroxide and dispersed (1 wt%) into a polyurethane matrix. The study of the photophysical behaviour shows that the Zn2Al LDH host enhances the chemical stability of the PdTPPC guest by minimizing photobleaching and quenching aggregation effects. The singlet oxygen production under irradiation of PdTPPC-Zn2Al/PU composite films is confirmed by the observation of an O2(1Δg) emission band centered at 1274 nm. Furthermore, the value of the rate constant kq for the PdTPPC phosphorescence quenching by oxygen kq = (8.2 ± 0.3) 10-2 s-1 Pa-1 indicates a slow diffusion of oxygen into and out of the PU polymer. In a second step, accelerating light ageing tests are conducted to determine the effect of singlet oxygen production on the chemical and mechanical stability of the PU matrix. Oxygen uptake experiments coupled with ATR-IR measurements indicate the probable formation of hydroxylated photoproducts but with no detrimental effects on the microstructure and the viscoelastic properties of the PU matrix as evidenced by dynamical mechanical analysis. Finally, in vitro preliminary antimicrobial tests show that PdTPPC-Zn2Al/PU composite films are able to inhibit S. aureus growth with no release of PdTPPC biocide from the PdTPPC-Zn2Al/PU composite film. We also observe a total inhibition of P. aeruginosa growth suggesting an efficacy against biofilm formation.

Assessment of the interrelation between photooxidation and biodegradation of selected polyesters after artificial weathering.

Three commercially available biodegradable polymers, two different aromatic-aliphatic copolyesters and polylactic acid, intended for the fabrication of agricultural mulching films, in addition to other applications, were subjected to a series of tests with the aim of studying the relationship between their photooxidation and biodegradation. Photooxidation resulted in the rearrangement of polymeric chains, in the case of both copolyesters the events led to polymeric chain crosslinking and the formation of insoluble polymeric gel. The tendency was significantly more pronounced for the copolyester with the higher content of the aromatic constituent. As regards polylactic acid photochemical reactions were not accompanied by crosslinking but instead provoked chain scissions. A biodegradation experiment showed that, despite marked structural changes, the extent of photooxidation was not the decisive factor, which significantly modified the rate of biodegradation in all three materials investigated. The specific surface area of the sample specimens was shown to be more important.

Strong interfacial attrition developed by oleate/layered double hydroxide nanoplatelets dispersed into poly(butylene succinate)

Poly(butylene succinate) (PBS) nanocomposite structure was studied as a function of the filler percentage loading. The resulting state of dispersion was evaluated by XRD and TEM, and the interfacial attrition between PBS chain and lamellar platelets by the melt rheological properties. Hybrid organic inorganic (O/I) layered double hydroxide (LDH) organo-modified by oleate anions was used as filler. It was found that the confinement supplied by the LDH framework forces the interleaved organic molecule to be more distant from each other than in the case of oleate salt, this having as an effect to decrease strongly the homonuclear intermolecular (1)H(1)H dipolar interaction. An additional consequence of this relatively free molecular rotation, affecting the (13)C CPMAS response as well, is to facilitate the delamination of the 2D-stacked layers during extrusion since an quasi-exfoliated PBS:Mg(2)Al/oleate structure is observed for filler loading lower than 5% w/w. This is in association to a non-linear viscoelasticity in the low-omega region and the observed shear-thinning tendency compares better than other PBS:silicate nanocomposite derivatives and is here explained by the presence of a percolated LDH nanoparticle network. Indeed the plastic deformation in the low-omega region is found to be restricted by well-dispersed LDH tactoids in association with a rather strong attrition phenomenon between tethered oleate anions and PBS chains.

Submicrometric characterization of the heterogeneous photooxidation of polypropylene by microthermal analysis

Abstract Photoageing of polymeric materials is known to induce physical and chemical modifications. Until recently the analysis of such modifications was realized in the bulk. The objective of this study is to quantify at a submicrometric level the physical heterogeneity induced by the photooxidation of polypropylene. In a first step, the impact of the photooxidation on the physical and chemical properties are quantified by bulk analysis (DSC and FTIR experiments) of a “homogeneous” photoaged material. In a second step, depth profile experiments are performed by microthermal analysis (μ-TA) and FTIR microscopy (μ-IR). Our main finding is to show that the physical properties of the material can be defined with a sub-micrometric resolution by μ-TA experiments, resolution which cannot be achieved with the usual spectrophotometric measurements.

Functionalisation of polybutylene succinate nanocomposites: from structure to reinforcement of UV-absorbing and mechanical properties

Cinnamic derivatives intercalated into ZnAl layered double hydroxides by coprecipitation are subsequently dispersed into a biodegradable polymer, polybutylene succinate (PBS). The structure and composition of the associated organic–inorganic hybrid assemblies are first characterized by X-ray diffraction (XRD) and UV spectroscopy, and then PBS extruded nanocomposite derivatives are evaluated against UV exposure. Using a combination of the PBS nanocomposite structures and the UV and rheological properties relationship, the effect of radiation time on the macromolecular changes undergone by the polymer chains, i.e. chain scissions and cross-linking, as well as on the UV-barrier evolution, is also scrutinized by means of transmission and emission spectroscopies. The combination of organically modified hydrotalcites with PBS could be used as an innovative route for sustainable development of UV protected materials and reduce the environmental impact of UV absorbing chemicals.

Identification of important abiotic and biotic factors in the biodegradation of poly(l-lactic acid).

The biodegradation of four poly(l-lactic acid) (PLA) samples with molecular weights (MW) ranging from approximately 34 to 160kgmol(-1) was investigated under composting conditions. The biodegradation rate decreased, and initial retardation was discernible in parallel with the increasing MW of the polymer. Furthermore, the specific surface area of the polymer sample was identified as the important factor accelerating biodegradation. Microbial community compositions and dynamics during the biodegradation of different PLA were monitored by temperature gradient gel electrophoresis, and were found to be virtually identical for all PLA materials and independent of MW. A specific PLA degrading bacteria was isolated and tentatively designated Thermopolyspora flexuosa FTPLA. The addition of a limited amount of low MW PLA did not accelerate the biodegradation of high MW PLA, suggesting that the process is not limited to the number of specific degraders and/or the induction of specific enzymes. In parallel, abiotic hydrolysis was investigated for the same set of samples and their courses found to be quasi-identical with the biodegradation of all four PLA samples investigated. This suggests that the abiotic hydrolysis represented a rate limiting step in the biodegradation process and the organisms present were not able to accelerate depolymerization significantly by the action of their enzymes.

Percolation network of organo-modified layered double hydroxide platelets into polystyrene showing enhanced rheological and dielectric behavior

A hybrid organic inorganic layered double hydroxide incorporating 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) is characterized by means of XRD, FTIR, and XPS. The in situ polymerization is scrutinized by 13C CPMAS as well as by a set of XRD experiments with varying temperature. It is found that the in situ polymerization is complete at 200 °C, and the hybrid framework sustains temperatures as high as 350 °C. Direct incorporation of poly(AMPS) is reported and the resulting hybrid LDH phases studied. Subsequently, all generated hybrid platelets are used as organo-modified 2D-type filler dispersed into polystyrene (PS). An immiscible PS composite structure with salient gel-like viscoelastic properties is obtained after bulk polymerization. In the low-frequency region, the typical Newtonian flow behaviour of PS is found to change progressively against filler loading into a shear-thinning behaviour evidenced by a pseudo-plateau in the elastic and loss modulus curves and associated with a shift of the glass transition temperature of PS to higher temperature. It is interpreted by hybrid LDH platelet domains presenting a large interface with the polymer, thus having the effect of restricting the plastic deformation by obstructing polymer chain motion. Such dispersed hybrid LDH tactoids forming a three-dimensional percolated network are indirectly evidenced by the enhancement of the dielectric properties illustrated by an increase in bulk dc conductivity of about one order at room temperature and in the dissipation factor. The study shows that hybrid LDH assembly is of relevance in topical applications regarding mechanical reinforcement as well as electrostatic energy dissipation.

A comprehensive study of an unusual jammed nanocomposite structure using hybrid layered double hydroxide filler

Polystyrene nanocomposites using hybrid organic inorganic (O/I) layered double hydroxide (LDH) and 4[12-(methacryloylamino)dodecanoylamino]benzenesulfonate (MADABS) interleaved molecules were studied as a function of the filler miscibility, dispersion, and the rheological behavior. Incorporation of the I/O filler gave rise to an expanded intercalated PS nanocomposite structure, while an immiscible structure was obtained after a thermal pre-treatment. However the utmost non-linear viscoelasticity in the low-omega region was obtained from the immiscible PS nanocomposite structure. Indeed, the presence of a sub-micrometer percolated structure was here depicted resulting in a jammed structure that progressively changed the typical low-frequency Newtonian flow behavior of PS to a shear-thinning behavior against the filler percentage, having as a consequence to restrict the plastic deformation in the low-omega region by obstructing polymer chain motion. From several characterizations XRD, TEM, and rheology, we demonstrated the presence of LDH agglomerates in spite of PS chain crawling in between the layers, whereas the apparent immiscible structure was composed of well dispersed LDH tactoids forming a three-dimensional percolated network. The gel-like behavior illustrated by the frequency power law dependence of the complex viscosity |eta(*)| proportional to omega(n), n approximately = -0.75 at 10 wt% of MADABS/LDH hybrid filler was then explained by the interconnected and concatenated hybrid LDH platelets domains developing an interfacial attrition with PS chains.