In Situ Dispersion of Lignin in Polypropylene via Supercritical CO2 Extrusion Foaming: Effects of Lignin on Cell Nucleation and Foam Compression Properties.

Supercritical CO2 (scCO2) extrusion foamed high-melt-strength (HMS) polypropylene (PP) often suffers from low cell density, large cell sizes, and poor cell structure uniformity due to the poor nucleation rates of CO2 in the PP. To remedy this, various inorganic fillers have been used as heterogeneous nucleation agents. Although their efficient nucleation effects have been demonstrated, the preparation of these fillers causes some adverse effects on the environment/human health or involves relatively expensive processes or non-eco-friendly chemicals. In this work, biomass-based lignin is studied as a sustainable, lightweight, and cost-effective nucleating agent. It is found that scCO2 could assist in situ dispersion of lignin in the PP in the foaming process, leading to significantly increased cell density, smaller cells, and improved cell uniformity. The Expansion Ratio is also simultaneously improved due to reduced diffusive gas loss. The PP/lignin foams with low lignin loadings exhibit higher compression moduli and plateau strengths than the PP foams with the same densities owing to the improved cell uniformity and probably also the reinforcing effect of the small lignin particles in cell walls. Moreover, the energy absorption capability of the PP/lignin foam with 1 wt% lignin could match the PP foam with similar compression plateau strengths; even the density of the former is 28% lower than the latter. Therefore, this work provides a promising approach to a cleaner and more sustainable production of HMS PP foams.

Fracture Toughness and Elastic Modulus of Epoxy-Based Nanocomposites with Dopamine-Modified Nano-Fillers.

This paper examines the effect of surface treatment and filler shape factor on the fracture toughness and elastic modulus of epoxy-based nanocomposite. Two forms of nanofillers, polydopamine-coated montmorillonite clay (D-clay) and polydopamine-coated carbon nanofibres (D-CNF) were investigated. It was found that Young's modulus increases with increasing D-clay and D-CNF loading. However, the fracture toughness decreases with increased D-clay loading but increases with increased D-CNF loading. Explanations have been provided with the aid of fractographic analysis using electron microscope observations of the crack-filler interactions. Fractographic analysis suggests that although polydopamine provides a strong adhesion between the fillers and the matrix, leading to enhanced elastic stiffness, the enhancement prohibits energy release via secondary cracking, resulting in a decrease in fracture toughness. In contrast, 1D fibre is effective in increasing the energy dissipation during fracture through crack deflection, fibre debonding, fibre break, and pull-out.

Simultaneous enhancements of UV resistance and mechanical properties of polypropylene by incorporation of dopamine-modified clay.

Inspired by the radical scavenging function of melanin-like materials and versatile adhesive ability of mussel-adhesion proteins, dopamine-modified clay (D-clay) was successfully incorporated into polypropylene (PP) using an amine-terminated PP oligomer as the compatibilizer. Although the PP/D-clay nanocomposites exhibit intercalated morphology, the incorporation of D-clay greatly improves the thermo-oxidative stability and UV resistance of PP owing to the strong radical scavenging ability of polydopamine (PDA) and large contact area between PP and the PDA coating on clay mineral. Moreover, the reinforcement effect brought by D-clay is fairly significant at very low clay loadings probably owing to the strong interfacial interactions between the layered silicates and the compatibilizer as well as that between the compatibilizer and the PP matrix. The work demonstrates that D-clay is a type of promising nanofiller for thermoplastics used for outdoor applications since it stabilizes and reinforces the polymers simultaneously.

Reinforcement of polyether polyurethane with dopamine-modified clay: the role of interfacial hydrogen bonding.

Dopamine-modified clay (D-clay) was successfully dispersed into polyether polyurethane (PU) by solvent blending. It is found that the incorporation of D-clay into PU gives rise to significant improvements in mechanical properties, including initial modulus, tensile strength, and ultimate elongation, at a very low clay loading. The large reinforcement could be attributed to the hydrogen bonds between the hard segments of PU and stiff D-clay layers that lead to more effective interfacial stress transfer between the polymer and D-clay. Besides, the interactions between D-clay and PU are also stronger than those between Cloisite 30B organoclay and the PU chains. Consequently, at a similar clay loading, the PU/D-clay nanocomposite has much higher storage modulus than the PU/organoclay nanocomposite at elevated temperatures.

A biomimetic approach to enhancing interfacial interactions: polydopamine-coated clay as reinforcement for epoxy resin.

A facile biomimetic method was developed to enhance the interfacial interaction in polymer-layered silicate nanocomposites. By mimicking mussel adhesive proteins, a monolayer of polydopamine was constructed on clay surface by a controllable coating method. The modified clay (D-clay) was incorporated into an epoxy resin, it is found that the strong interfacial interactions brought by the polydopamine benefits not only the dispersion of the D-clay in the epoxy but also the effective interfacial stress transfer, leading to greatly improved thermomechanical properties at very low inorganic loadings. Rheological and infrared spectroscopic studies show that the interfacial interactions between the D-clay and epoxy are dominated by the hydrogen bonds between the catechol-enriched polydopamine and the epoxy.

Packing behaviors of structurally different polyhedral oligomeric silsesquioxane-imidazolium surfactants in clay.

This paper reports the packing structures of two types of polyhedral oligomeric silsesquioxane (POSS)-imidazolium surfactants with different molecular rigidity in the intergalleries of montmorillonite clay. Wide-angle X-ray scattering (WAXS) and molecular modeling studies suggest that the POSS-imidazolium cations have a bilayer packing structure in clay with the long axes of the molecules largely tilted with respect to the basal plane. Direct evidence for the bilayer structure is provided by transmission electron microscopy (TEM). WAXS and differential scanning calorimetry (DSC) results indicate that the relatively flexible POSS-imidazolium cation is able to form a two-dimensionally ordered structure in the clay intergalleries, while the relatively rigid one exhibits a disordered structure in clay. Furthermore, with reducing surfactant loading, the clay modified with the rigid surfactant exhibits increased interlayer d-spacings probably because the surfactant is able to take more extended conformation at lower loadings. With its low organic content and disordered surfactant packing structure, the clay modified with the rigid surfactant also exhibits excellent thermal and thermo-oxidative stabilities.

Poly(ethylene terephthalate)/clay nanocomposites based on aminododecanoic acid-modified clay: effect of compatibilizer reactivity on clay dispersion.

Poly(ethylene terephthalate) (PET)/Clay hybrids were prepared via in situ polymerization, in which the clay was modified with 12-aminododecanoic acid (ADA). Three types of bifunctional compounds were introduced into the system, respectively, as compatibilizers between PET and ADA-Clay. The three compounds contain 1 degree, 2 degree, and 3 degree amino groups, respectively, that could form ionic complex with carboxylic acid of ADA. They also contain an ester group that could react with PET chains through transesterification. The results show that adding the compound with 3 degree amino group can improve clay dispersion significantly, while the ones with 1 degree and 2 degree amino groups are not effective compatibilizers. The possible underlying mechanism is discussed.