Anders Hult

Residual stress build-up in thermoset films cured above their ultimate glass transition temperature

The stress build-up during isothermal cure below the ultimate glass transition temperature of epoxy and acrylate films is investigated in detail. Four systems are studied; two acrylates and two epoxies, with different crosslink densities. Relaxation modulus and film shrinkage are measured simultaneously during cure. The stress build-up is measured independently using a bi-layer beam bending technique. A model for the build-up of cure stresses is proposed, in which stresses are generated by the cure shrinkage and decay by viscoelastic relaxation. The relaxation is described by a simple, modified Maxwell model. Owing to the absence of memory in the Maxwell model, the resulting equation is simple and numerical stress computation straightforward. The stress build-up over time is thus simulated for the four model systems based on the relaxation and shrinkage data, and the simulations compared with the experimentally observed stress build-up. The model successfully predicts the cure stresses where more standard elastic methods fail. It is found that the amount of stress build-up during cure varies greatly between the different systems. In general, a higher crosslink density results in higher stress build-up. The stress on cure ranged from less than 1% of the total stress on cure and cool-down in a lightly crosslinked epoxy to more than 30% of the total stress in densely crosslinked epoxies and acrylates. Finally simple approximations for estimating the stress levels after cure and cool-down from basic material properties, e.g. modulus and cure shrinkage, are proposed.

Synthesis of hyperbranched aliphatic polyethers via cationic ring-opening polymerization of 3-ethyl-3-(hydroxymethyl)oxetane

Thermally initiated cationic ring-opening polymerization of 3-ethyl-3-(hydroxymethyl)oxetane was carried out using benzyltetramethylenesulfonium hexafluoroantimonate as initiator. The resulting hydroxy-functional polyether was thoroughly analyzed by 1H and 13C NMR spectroscopy and found to have a hyperbranched architecture with a degree of branching of 0.4. The polyether was successfully employed as a multifunctional initiator for e-caprolactone. Molecular weight measurements on the polyether showed a narrow molecular weight distribution analyzed by SEC and MALDI-TOF (1.3 and 1.4, respectively).

Bifunctional Dendrimers: From Robust Synthesis and Accelerated One‐Pot Postfunctionalization Strategy to Potential Applications

A fourth wheel: Two sets of bifunctional AB(2)C dendrimers having internal acetylene/azides and external hydroxy groups were constructed utilizing benign synthetic protocols. An in situ postfunctionalization strategy was successfully carried out to illustrate the chemoselective nature of these dendrimers. The dendrimers were also transformed into dendritic nanoparticles or utilized as dendritic crosslinkers for the fabrication hydrogels.

Superhydrophobic and self-cleaning bio-fiber surfaces via ATRP and subsequent postfunctionalization

Superhydrophobic and self-cleaning cellulose surfaces have been obtained via surface-confined grafting of glycidyl methacrylate using atom transfer radical polymerization combined with postmodification reactions. Both linear and branched graft-on-graft architectures were used for the postmodification reactions to obtain highly hydrophobic bio-fiber surfaces by functionalization of the grafts with either poly(dimethylsiloxane), perfluorinated chains, or alkyl chains, respectively. Postfunctionalization using alkyl chains yielded results similar to those of surfaces modified by perfluorination, in terms of superhydrophobicity, self-cleaning properties, and the stability of these properties over time. In addition, highly oleophobic surfaces have been obtained when modification with perfluorinated chains was performed.

Stability and biocompatibility of a library of polyester dendrimers in comparison to polyamidoamine dendrimers

Dendrimers can be designed for several biomedical applications due to their well-defined structure, functionality and dimensions. The present study focused on the in vitro biocompatibility evaluation of a library of aliphatic polyester dendrimers based on 2,2-bis(methylol)propionic acid (bis-MPA) with an overall diameter of 0.5-2 nm. In addition, dendrimers with two different chemical surfaces (neutral with hydroxyl end group and anionic with carboxylic end group) and dendrons corresponding to the structural fragments of the dendrimers were evaluated. Commercial polyamidoamine dendrimers (PAMAM) with cationic (amine) or neutral (hydroxyl) end group were also included for comparison. Cell viability studies were conducted in human cervical cancer (HeLa) and acute monocytic leukemia cells (THP.1) differentiated into macrophage-like cells as well as in primary human monocyte-derived macrophages. Excellent biocompatibility was observed for the entire hydroxyl functional bis-MPA dendrimer library, whereas the cationic, but not the neutral PAMAM exerted dose-dependent cytotoxicity in cell lines and primary macrophages. Studies to evaluate material stability as a function of pH, temperature, and time, demonstrated that the stability of the 4th generation hydroxyl functional bis-MPA dendrimer increased at acidic pH. Taken together, bis-MPA dendrimers are degradable and non-cytotoxic to human cell lines and primary cells.

Synthesis of Polycaprolactone-Grafted Microfibrillated Cellulose for Use in Novel Bionanocomposites–Influence of the Graft Length on the Mechanical Properties

In the present work, microfibrillated cellulose (MFC) made from bleached sulfite softwood dissolving pulp was utilized to reinforce a poly(ε-caprolactone) (PCL) biopolymer matrix. To improve the dispersibility of the hydrophilic MFC in the nonpolar matrix and the interfacial adhesion in the composite material, we covalently grafted the MFC with PCL via ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). To be able to investigate the effect of the PCL graft length on the mechanical properties of the composite material, we performed ROP to different molecular weights of the grafts. Bionanocomposites containing 0, 3, and 10 wt % MFC were prepared via hot pressing using both unmodified and PCL grafted MFC (MFC-g-PCL) as reinforcement. PCL grafting resulted in improved dispersion of the MFC in a nonpolar solvent and in the PCL matrix. The mechanical testing of the biocomposites showed an improvement in the mechanical properties for the PCL grafted MFC in comparison to ungrafted MFC. It was also shown that there was an impact on the mechanical properties with respect to the PCL graft lengths, and the strongest biocomposites were obtained after reinforcement with MFC grafted with the longest PCL graft length.

Use and interpretation of scratch tests on ductile polymer coatings

The use and interpretation of contact scratch tests on polymer coatings has been investigated. The influences from test parameters such as scratch speed, contact geometry and load on the deformation response were examined. Two ductile polymer coatings of commercial grade tailored for pre-painted steel applications were used as model systems. The residual deformation pattern was examined with optical microscopy, white-light interferometry, and atomic force microscopy. Free-standing coating films were also subjected to static, transient and dynamic tensile testing to find a correlation between the intrinsic coating properties and the scratch behavior. The results indicate that the use of a single set of contact parameters is insufficient to reflect the overall response of a coating material to real contact conditions. A well-designed scratch test will however give a substantial amount of useful information.

The effect of degree of branching on the rheological and thermal properties of hyperbranched aliphatic polyethers

A series of hyperbranched aliphatic polyethers with different degree of branching (DB) and molecular weights have been studied with respect to their rheological and thermal properties. The DB was shown to affect the ability of the polymers to crystallize and thereby also the rheological properties of the polymers. A low DB resulted in semi-crystalline polymers with melting points between 100 and 130°C. The polymers with a higher DB were essentially amorphous and behaved as non-entangled Newtonian liquids in the molten state.

Synthesis and characterisation of star branched polyesters with dendritic cores and the effect of structural variations on zero shear rate viscosity

A series of branched polyesters consisting of poly(epsilon-caprolactone) (PCL) (degree of polymerisation: 5-200) initiated from hydroxy-functional cores and end-capped with methylmethacrylate have ...

Relaxation processes in hyperbranched polyesters: Influence of terminal groups

Abstract Three hyperbranched polyesters with the same backbone structure but with different terminal groups: hydroxyl, benzoate or acetate groups, were studied by dielectric spectroscopy, differential scanning calorimetry and dynamic mechanical analysis. The benzoate- and acetate-terminated polymers exhibited only one subglass process (β), originating from reorientation of the ester groups, distinct from the glass transition (α). The hydroxyl-terminated sample exhibited a low-temperature subglass process (γ), due to motions of the hydroxyl groups, in addition to the β and α processes. The relaxation strengths of the hyperbranched polymers were found to be considerably lower than for those of linear analogues. The activation energies of the β process in the polymers studied increased in the order of hydroxyl, acetate and benzoate, indicating that the benzoate-terminated polymer is the most constrained.