Unsaturated,biobased polyesters and their cross‐linking via radical copolymerization

Biobased, unsaturated polyesters derived from isosorbide, maleic anhydride, and succinic acid were synthesized and characterized. The presence of maleic anhydride units in the structure of the polyesters allowed converting them into cured coatings by radical copolymerization with crosslinking agents such as 2‐hydroxyethyl methacrylate, N‐vinyl‐2‐pyrrolidinone, acrylic acid or methacrylamide. The investigated polyesters were obtained via bulk polycondensation, catalyzed by titanium(IV) n‐butoxide. 2D NMR and MALDI‐Tof‐MS spectroscopy proved that this polymerization resulted in isomerization of maleic acid units into fumaric ones and in the formation of slightly branched structures by the reaction of isosorbide (end) groups with main chain unsaturated bonds. Moreover, some double bonds proved to have reacted with the condensation by‐product water. The resulting polyesters displayed the expected correlation between variables such as molecular weight and content of unsaturated bonds and their T_g values. Since the thermal properties of the obtained polyesters were appropriate for coating applications, the polymers were crosslinked with unsaturated monomers by radical copolymerization. The crosslinking process was studied using FTIR spectroscopy and by measurements of the soluble part of the cured coatings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2885–2895, 2010     

Bioactive Sol-Gel Coatings for Orthopaedic Prosthesis

Sol-gel materials have been proposed in last years for clinical applications. In this work, bioactive sol-gel coatings were prepared from suspensions of up to 25% wt. of bioactive glass (CaO·SiO₂·P₂O₅) particles in a hybrid sol obtained from TEOS and MTES. Thick dip-coatings showed in vitro bioactivity after a few days, but glass-particles dissolution promotes a slight reduction in the corrosion resistance. In order to overpass this problem, a two-stage sol-gel coating system that includes a first SiO₂ hybrid film, acting as barrier against corrosion, and an external bioactive layer from glass particle suspension is proposed. The obtained samples revealed significant improvement in their electrochemical behaviour, and showed in vitro bioactivity.     

Chemical stability of TiN,TiAlN and AlN layers in aggressive SO2 environments

In this paper, we have studied, using X‐ray photoelectron spectroscopy (XPS), the chemical stability of TiN, TiAlN and AlN layers produced by magnetron sputtering on Si wafer substrates, against humid, SO₂‐polluted atmospheres. The results have indicated that the TiN layers suffer almost no degradation after seven days of exposure to the aggressive environment. The degradation of the TiAlN layers is small, and this is evidenced by the appearance of signals corresponding to N? O bonds in the N 1s spectra, after seven days of exposure to the corrosive atmosphere and the increase in the Ti 2p spectra of the contribution corresponding to TiO₂. In contrast, the degradation experienced by the AlN layers is quite large. The spectra reveal dramatic changes after just one day of exposure to the aggressive conditions. This is related to the preferential growth of the AlN layers, which gives rise to an open, columnar structure. Copyright © 2005 John Wiley & Sons, Ltd.     

光盘用2P胶应用研究进展

对光盘用２Ｐ胶的应用研究进展情况进行了评述，其中光盘制备用光聚合浮雕成型２Ｐ胶的基本组成为各类多官能团丙烯酸酯类单体；光盘保护涂层用２Ｐ胶主要组分为环氧丙烯酸酯类预聚体。     

On the combined use of scratch tests and CLA profilometry for the characterization of polyester powder coatings: Influence of scratch load and speed

The prediction of the mechanical properties of polyester powder coatings is of paramount importance, as they have to undergo a wide variety of forces and deformations during their service life. Determine the response of polymeric coatings to the actual loading conditions can be, however, very troublesome as their properties are function of the material physical state, rate-dependence and yield and break behaviour. Further, the characterization of soft, contaminated organic surfaces such as polymers can often cause severe problems with reliability and imaging accuracy due to instrumental artefacts.This is therefore the context in which this paper investigates the capability of multiple parameters scratch tests joined with non-contact CLA profilometry and FE-SEM to detect the scratch response of polyester powder coatings for protective and decorative outdoor applications. Scratch tests with blunt contact geometry were used to evaluate the response of polyester coatings baked at different time-temperature programs and, so, at different stages of their curing process. In particular, being such coatings highly non-linear in their response to mechanical stress or strain, the influence from scratch load and speed was carefully taken into account. Analytical evaluations of the experimental results led to good correlations between the extent of the deformed zone after scratch, scratch parameters and curing operational settings. This allows mapping the scratch response of the polyester topcoats to broad ranges of both scratch parameters and curing conditions.     

Conductivity of crosslinked low surface energy epoxy coatings

A new and straightforward method has been studied to prepare crosslinked low surface energy semiconductive epoxy coatings. The low surface energy is obtained by adding a small amount of partially fluorinated bifunctional primary amine Jeffamine D230 crosslinker and the conductivity is achieved by adding a small amount of semiconductive nanosized Cobalt(III) phthalocyanine particles. The use of partially fluorinated crosslinker strongly influences the conductivity, the conductive particle network structure, and the network distribution in the coatings. Compared to coatings that are free of fluorine, variations in fractal dimension, percolation threshold, particle‐containing layer thickness, and conductivity level are observed as the amount of fluorinated species is varied. These differences can be explained by (local) differences in effective Hamaker constant, viscosity, curing rate, evaporation of the solvent, and presence or absence of polymer matrix between the particles in the network. Our results suggest that other crosslinked semiconductive low surface energy epoxy coatings can be realized in a similar manner, but careful optimization of processing conditions is required to obtain the desired conductivity levels at low filler concentration. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Chem 47: 366–380, 2009     

Isomer‐dependent properties of poly(vinyl pyridine)‐based films grown on copper surfaces

The effect of poly(2‐vinyl pyridine) (P2VP) and poly(4‐vinyl pyridine) (P4VP) isomers on the growth of surface films on copper substrates was studied by electrochemical, spectroscopic, thermogravimentric, and microscopic methods. In acid environment (3% v/v acetic acid) and in the presence of KSCN, electrochemically generated copper cations reacted rapidly with SCN^? and P2VP or P4VP, yielding coordination compounds, which deposited onto copper surfaces as films. The characteristics of such polymer–metal complexes (films) were markedly isomer‐dependent. Cu(I)/P2VP/SCN^? complexes with monovalent cations and sulfur‐coordinated thiocyanate were obtained in the presence of P2VP, whereas the formation of Cu(II)/P4VP/SCN^? complexes with divalent cations and nitrogen‐coordinated thiocyanate was observed in the presence of P4VP. Interestingly, similar physical–chemical properties (electronic structure, stoichiometry, and thermal behavior) were observed for materials synthesized by electrochemical and chemical methods. These results suggest, therefore, that control over the surface properties of copper substrates can be achieved using electrosynthesized films based on different PVP isomers. Besides acting as effective protective barriers against aggressive media and thus reducing the metal dissolution (corrosion) kinetics, these materials are potentially attractive for other applications in which surface properties are paramount, such as in catalysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 215–225, 2009     

Preparation of cationic latices comprising hollow thermostable particles

A method is described for the preparation of cationic latices comprising submicron hollow particles for a possible application as a thermally stable polymeric pigment in coatings or pigmented compositions on the basis of thermosetting polymers cured at temperatures up to 170–190 °C. The method is based on the deposition of melamine–formaldehyde resin in the form of cationic colloid onto anionic hollow particles resulting in the recharging of anionic hollow particles and the formation of an outer melamine shell, which provides thermal stability of the hollow particles at curing and application of pigmented coatings and compositions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2225–2234, 2004