Viscoelastic effects on the scratch resistance of polymers: relationship between mechanical properties and scratch properties at various temperatures

Scratch durability of polymer surfaces and coatings is becoming critical for the increasing use of these materials in new applications, replacing other materials with harder surfaces.

Scratch resistance of polymers has been the subject of numerous studies, which have led to specific definitions for plastic deformation characterization and fracture resistance during scratch testing. Viscoelastic and viscoplastic behavior during a scratch process have been related to dynamic mechanical properties that can be measured via dynamic nano-indentation testing. Yet, the understanding of the origin of the fracture process of a polymer during scratch remains approximate. Parameters like tip shape and size, scratch velocity and loading rate, applied strain and strain rates, have been considered critical parameters for the fracture process, but no correlation has been clearly established.

The goal of this work is to define and analyze scratch parameters that relate to mechanical properties. The evolution of scratch resistance parameters as a function of temperature and strain rate, compared to the evolution of dynamic mechanical properties obtained from indentation and uniaxial tensile tests over a range of temperature for poly(methyl methacrylate) (PMMA) helped in identifying a correlation between the tensile stress–strain behavior and scratch fracture toughness.

This correlation brings a new understanding of the origin of the fracture mechanisms during a scratch process. In particular, it is demonstrated that the characteristic strain applied by the indenter is a most relevant parameter to describe the fracture resistance during a scratch process, independently of the indenter geometry.     

Behavior of silica aerogel networks as highly porous solid solvent media for lipases in a model transesterification reaction

Highly porous silica aerogels with differing balances of hydrophobic and hydrophilic functionalities were studied as a new immobilization medium for enzymes. Two types of lipases from Candida rugosa and Burkholderia cepacia were homogeneously dispersed in wet gel precursors before gelation. The materials obtained were compared in a simple model reaction: transesterification of vinyl laurate by 1-octanol. To allow a better comparison of the hydrophobic/hydrophilic action of the solid, very open aerogel networks with traditional organic hydrophobic/hydrophilic liquid solvents, this reaction was studied in mixtures containing different proportions of 2-methyl-2-butanol, isooctane, and water. The results are discussed in relation to the porous and hydrophobic nature of aerogels, characterized by nitrogen adsorption. It was found that silica aerogels can be considered as "solid" solvents for the enzymes, able to provide hydrophobic/hydrophilic characteristics different from those prevailing in the liquid surrounding the aerogels. A simple mechanism of action for these aerogel networks is proposed.     

Expanding the Genetic Code in Xenopus laevis Oocytes

Heterologous expression of ligand‐gated ion channels (LGICs) in Xenopus laevis oocytes combined with site‐directed mutagenesis has been demonstrated to be a powerful approach to study structure–function relationships. In particular, introducing unnatural amino acids (UAAs) has enabled modifications that are not found in natural proteins. However, the current strategy relies on the technically demanding in vitro synthesis of aminoacylated suppressor tRNA. We report here a general method that circumvents this limitation by utilizing orthogonal aminoacyl‐tRNA synthetase (aaRS)/suppressor tRNA_CUA pairs to genetically encode UAAs in Xenopus oocytes. We show that UAAs inserted in the N‐terminal domain of N‐methyl‐D ‐aspartate receptors (NMDARs) serve as photo‐crosslinkers that lock the receptor in a discrete conformational state in response to UV photo treatment. Our method should be generally applicable to studies of other LGICs in Xenopus oocytes.     

Polymer stain resistance: Prediction versus experiment

The coloration of different polymer films (from commodity and packaging films to performance films) by contact with various food coloring substances was evaluated. For this purpose, both solubility parameters as a prediction tool, and immersion experiments for time range between 24 and 1000 h were established. The two predicting tools are the Hoy and Hoftyzer‐Van Krevelen (HVK) methods. For PE and PP, HVK's method is preferred for predicting coloration. Neither of the HVK's and Hoy's methods was able to establish a coloration prediction for PET while both methods could predict the staining of PEEK. The coloration of partially and fully fluorinated polymers is well predicted by the Hoy's method. The behavior of PP/PA and PP/PA/PP multilayer films was also studied. Crystallinity degree of polymers, temperature and concentration of coloring molecules are also important parameters, which are not taken into account in solubility theories. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Phase Separation and Spatial Morphology in Sodium Silicate Glasses by AFM,Light Scattering and NMR

The morphological and structural properties of sodium silicate (Na₂O–SiO₂) glasses were analyzed using atomic force microscopy (AFM) and light scattering following thermal treatments. AFM observations indicated that the glass surface microstructure evolves during the phase separation mechanisms from continuous interpenetrating phases in the spinodal decomposition process to separated droplets embedded in a continuous matrix for the nucleation/growth one. Raman mapping gave evidence of a phase separation through the nucleation/growth process with formation of silica‐rich clusters characterized by higher polymerization degree as separate droplets. The variations in inhomogeneities versus temperature investigated by Brillouin are exponential for spinodal decomposition and linear in the case of nucleation/growth mechanism. Nuclear magnetic resonance spectroscopy was used to investigate the spatial distribution of the various Q_n species present in thermally treated glasses and allows determining fractal dimension between two and three.     

A 3D EFFECT IN THE WEDGE ADHESION TEST: APPLICATION OF SPECKLE INTERFEROMETRY

The wedge test is of considerable use for evaluating adhesion between two bonded rigid substrates. In its (usual) static form, release of elastic strain energy is equated to effective adhesion energy during crack growth. However, the test is usually treated as two-dimensional. In fact, it is really three-dimensional due to anticlastic bending effects of the bent beam(s) during crack propagation.

We studied a composite material/epoxy/aluminium alloy system and observed a curved crack front during propagation. This leads to doubt as to the value of crack length to be inserted in the adhesion energy formula. In addition, by using the highly sensitive technique of speckle interferometry, it was possible to study anticlastic bending effects in a quantitative manner. Far from the crack front, agreement between theory and experimental is good, yet work remains to be done to understand the zone near the fracture zone.     

Performance of exterior semitransparent PVDF–acrylic coatings

The purpose of this study was to investigate the performance of a semitransparent PVDF–acrylic coating on two wood species: Black spruce and White pine. An accelerated aging test was performed on the PVDF–acrylic coating and the results obtained were compared with those obtained for a water-based acrylic coating. Color changes were found to be more significant for the acrylic coating, especially after 1000 h of exposure, and for the White pine panels. Infrared spectroscopy revealed that the acrylic resin was more affected by the accelerated aging test than the PVDF resin, although X-ray photoelectron spectroscopy revealed that PVDF was slightly affected at the extreme surface (first 10 nm). Star-shaped defects were found at the surface of the White pine panels finished with the PVDF–acrylic coating. Experiments revealed that the PVDF–acrylic coating does not seem to be flexible enough to sustain resin exudation or other stresses.     

Dendrimers or Nanoparticles as Supports for the Design of Efficient and Recoverable Organocatalysts?

The Jørgensen–Hayashi catalyst [(S)‐α,α‐diphenylprolinol trimethylsilyl ether] was grafted onto the surface of two different supports: phosphorus dendrimers (generations 1 to 3) and magnetic, polymer‐coated cobalt/carbon (Co/C) nanobeads. These new supported catalysts displayed high activities and selectivities in the Michael additions of a wide range of aldehydes to different nitroolefins. Moreover, the dendrimer of the third generation displayed excellent recycling abilities since it could be recovered and reused in 7 consecutive runs without loss of activity.