Patrizio Raffa

The effect of hydrophilic and hydrophobic block length on the rheology of amphiphilic diblock Polystyrene-b-Poly(sodium methacrylate) copolymers prepared by ATRP

Following our previous investigation on the effect of molecular architecture on the rheology of Polystyrene-b-Poly(sodium methacrylate) copolymers (PS-b-PMAA), we consider here diblock PS-b-PMAA copolymers characterized by a different length of either the hydrophilic or the hydrophobic block. Various copolymers characterized by different PS or PMAA block length have been prepared by ATRP (kinetics is also discussed) and studied from the point of view of their rheological behaviour in water. To the best of our knowledge, this is the first systematic investigation concerning the effect of block length on the rheology of diblock polyelectrolytes. We found that the hydrophobic block length has small influence on the rheology. Surprisingly, the polymers with shortest PMAA blocks yield the strongest gels at high concentration. A simple model based on the classical theories of self-assembly and percolation of amphiphilic polymers has been here developed in order to explain the observed data.

Electrodeposition of Y2O3–Au composite coatings for SOFC interconnects: in situ monitoring of film growth by surface enhanced Raman spectroscopy

Abstract In this paper, the authors report in situ surface enhanced Raman spectroscopy (SERS) experiments carried out during the electrochemical deposition of Y2O3/Au from chloride salts dissolved in hydroalcoholic solutions containing chitosan as a binder. This composite was recently proposed by the authors as an electronically conducting coating able to protect AISI 430 interconnects from hot corrosion in SOFC cathodic environment. Dynamic SERS spectra were obtained during galvanostatic electrodeposition, showing peaks in the typical Raman shift range of M–O stretching and bending vibrations that have been tentatively assigned on the basis of quantum-chemical computations. The time dependence of the spectral features can be followed with a simple kinetic model accounting for the pH transient occurring in the catholyte.

An easy synthetic way to exfoliate and stabilize MWCNTs in a thermoplastic pyrrole-containing matrix assisted by hydrogen bonds

This work focuses on the design of an engineered thermoplastic polymer containing pyrrole units in the main chain and hydroxyl pendant groups (A-PPy-OH), which help in achieving nanocomposites containing well-distributed, exfoliated and undamaged MWCNTs. The thermal annealing at 100 °C of the pristine nanocomposite promotes the redistribution of the nanotubes in terms of a percolative network, thus converting the insulating material in a conducting soft matrix (60 μΩ m). This network remains unaltered after cooling to r.t. and successive heating cycles up to 100 °C thanks to the effective stabilization of MWCNTs provided by the functional polymer matrix. Notably, the resistivity–temperature profile is very reproducible and with a negative temperature coefficient of −0.002 K−1, which suggests the potential application of the composite as a temperature sensor. Overall, the industrial scale by which A-PPy-OH can be produced offers a straightforward alternative for the scale-up production of suitable polymers to generate multifunctional nanocomposites.

Effect of the Polyketone Aromatic Pendent Groups on the Electrical Conductivity of the Derived MWCNTs-Based Nanocomposites

Electrically conductive plastics with a stable electric response within a wide temperature range are promising substitutes of conventional inorganic conductive materials. This study examines the preparation of thermoplastic polyketones (PK30) functionalized by the Paal–Knorr process with phenyl (PEA), thiophene (TMA), and pyrene (PMA) pendent groups with the aim of optimizing the non-covalent functionalization of multiwalled carbon nanotubes (MWCNTs) through π–π interactions. Among all the aromatic functionalities grafted to the PK30 backbone, the extended aromatic nuclei of PMA were found to be particularly effective in preparing well exfoliated and undamaged MWCNTs dispersions with a well-defined conductive percolative network above the 2 wt % of loading and in freshly prepared nanocomposites as well. The efficient and superior π–π interactions between PK30PMA and MWCNTs consistently supported the formation of nanocomposites with a highly stable electrical response after thermal solicitations such as temperature annealing at the softening point, IR radiation exposure, as well as several heating/cooling cycles from room temperature to 75 °C.

Totally Organic Redox-Active pH-Sensitive Nanoparticles Stabilized by Amphiphilic Aromatic Polyketones

Amphiphilic aromatic polymers have been synthesized by grafting aliphatic polyketones with 4-(aminomethyl)benzoic acid at different molar ratios via the Paal-Knorr reaction. The resulting polymers, showing diketone conversion degree of 16%, 37%, 53%, and 69%, have been complexed with the redox-active 2,3,5-triphenyl-2H-tetrazolium chloride, a precursor molecule with which aromatic-aromatic interactions are held. Upon addition of ascorbic acid to the complexes, in situ reduction of the tetrazolium salt produced 1,3,5-triphenylformazan nanoparticles stabilized by the amphiphilic polymers. The stabilized nanoparticles display highly negative zeta potential [-(35-70) mV] and hydrodynamic diameters in the submicron range (100-400 nm). Nonaromatic polyelectrolytes or hydrophilic aromatic copolymers showing low linear aromatic density and high linear charge density such as acrylate/maleate and sulfonate/maleate-containing polymers were unable to stabilize formazan nanoparticles synthesized by the same method. The copolymers studied here bear uncharged nonaromatic comonomers (unreacted diketone units) as well as charged aromatic comonomers, which furnish amphiphilia. Thus, the linear aromatic density and the maximum linear charge density have the same value for each copolymer, and the hydrophilic/hydrophobic balance varies with the diketone conversion degree. The amphiphilia of the copolymers allows the stabilization of the nanoparticles, even with the copolymers showing a low linear aromatic density. The method of nanoparticle synthesis constitutes a simple, cheap, and green method for the production of switchable totally organic, redox-active, pH-sensitive nanoparticles that can be reversibly turned into macroprecipitates upon pH changing.

Effect of Rubber Polarity on Cluster Formation in Rubbers Cross-Linked with Diels–Alder Chemistry

Diels–Alder chemistry has been used for the thermoreversible cross-linking of furan-functionalized ethylene/propylene (EPM) and ethylene/vinyl acetate (EVM) rubbers. Both furan-functionalized elastomers were successfully cross-linked with bismaleimide to yield products with a similar cross-link density. NMR relaxometry and SAXS measurements both show that the apolar EPM-g-furan precursor contains phase-separated polar clusters and that cross-linking with polar bismaleimide occurs in these clusters. The heterogeneously cross-linked network of EPM-g-furan contrasts with the homogeneous network in the polar EVM-g-furan. The heterogeneous character of the cross-links in EPM-g-furan results in a relatively high Young’s modulus, whereas the more uniform cross-linking in EVM-g-furan results in a higher tensile strength and elongation at break.

Electrically-Responsive Reversible Polyketone/MWCNT Network through Diels-Alder Chemistry

This study examines the preparation of electrically conductive polymer networks based on furan-functionalised polyketone (PK-Fu) doped with multi-walled carbon nanotubes (MWCNTs) and reversibly crosslinked with bis-maleimide (B-Ma) via Diels-Alder (DA) cycloaddition. Notably, the incorporation of 5 wt.% of MWCNTs results in an increased modulus of the material, and makes it thermally and electrically conductive. Analysis by X-ray photoelectron spectroscopy indicates that MWCNTs, due to their diene/dienophile character, covalently interact with the matrix via DA reaction, leading to effective interfacial adhesion between the components. Raman spectroscopy points to a more effective graphitic ordering of MWCNTs after reaction with PK-Fu and B-Ma. After crosslinking the obtained composite via the DA reaction, the softening point (tan(δ) in dynamic mechanical analysis measurements) increases up to 155 °C, as compared to the value of 130 °C for the PK-Fu crosslinked with B-Ma and that of 140 °C for the PK-Fu/B-Ma/MWCNT nanocomposite before resistive heating (responsible for crosslinking). After grinding the composite, compression moulding (150 °C/40 bar) activates the retro-DA process that disrupts the network, allowing it to be reshaped as a thermoplastic. A subsequent process of annealing via resistive heating demonstrates the possibility of reconnecting the decoupled DA linkages, thus providing the PK networks with the same thermal, mechanical, and electrical properties as the crosslinked pristine systems.

Acetalised Galactarate Polyesters: Interplay between Chemical Structure and Polymerisation Kinetics

In spite of the progress that has made so far in the recent years regarding the synthesis of bio-based polymers and in particular polyesters, only few references address the optimisation of these new reactions with respect to conversion and reaction time. Related to this aspect, we here describe the transesterification reaction of two different acetalised galactarate esters with a model aliphatic diol, 1,6-hexanediol. The kinetics of these two apparently similar reactions is compared, with a focus on the conversion while varying the concentration of a di-butyltin oxide catalyst (DBTO), respectively, the used N2 flow-rate. During the first stage of polymerisation, the molecular weight of the end-products is more than doubled when using a 250 mL/min flow as opposed to an almost static N2 pressure. Additionally, the resulted pre-polymers are subjected to further polycondensation and the comparison between the obtained polyesters is extended to their thermal, mechanical and dielectrical characterisation. The influence of the acetal groups on the stability of the polyesters in acidic conditions concludes the study.

Thermoreversibly Cross-Linked EPM Rubber Nanocomposites with Carbon Nanotubes

Conductive rubber nanocomposites were prepared by dispersing conductive nanotubes (CNT) in thermoreversibly cross-linked ethylene propylene rubbers grafted with furan groups (EPM-g-furan) rubbers. Their features were studied with a strong focus on conductive and mechanical properties relevant for strain-sensor applications. The Diels-Alder chemistry used for thermoreversible cross-linking allows for the preparation of fully recyclable, homogeneous, and conductive nanocomposites. CNT modified with compatible furan groups provided nanocomposites with a relatively large tensile strength and small elongation at break. High and low sensitivity deformation experiments of nanocomposites with 5 wt % CNT (at the percolation threshold) displayed an initially linear sensitivity to deformation. Notably, only fresh samples displayed a linear response of their electrical resistivity to deformations as the resistance variation collapsed already after one cycle of elongation. Notwithstanding this mediocre performance as a strain sensor, the advantages of using thermoreversible chemistry in a conductive rubber nanocomposite were highlighted by demonstrating crack-healing by welding due to the joule effect on the surface and the bulk of the material. This will open up new technological opportunities for the design of novel strain-sensors based on recyclable rubbers.

Star-Like Branched Polyacrylamides by RAFT polymerization, Part II : Performance Evaluation in Enhanced Oil Recovery (EOR)

In the present study the performance of a series of star-like branched polyacrylamides (SB-PAMs) has been investigated in oil recovery experiments to ultimately determine their suitability as novel thickening agent for enhanced oil recovery (EOR) applications. Hereby, SB-PAMs were compared with conventional linear PAM. The effect of a branched molecular architecture on rheology, and consequently on oil recovery was discussed. Rheological measurements identified unique properties for the SB-PAMs, as those showed higher robustness under shear and higher salt tolerance than their linear analogues. EOR performance was evaluated by simulating oil recovery in two-dimensional flow-cell measurements, showing that SB-PAMs perform approximately 3–5 times better than their linear analogues with similar molecular weight. The salinity did not influence the solution viscosity of the SB-PAM, contrarily to what happens for partially hydrolyzed polyacrylamide (HPAM). Therefore, SB-PAMs are more resilient under harsh reservoir conditions, which can make them attractive for EOR applications.