Adriana Nicoleta Frone

Morphology and thermal properties of PLA-cellulose nanofibers composites.

Biodegradable nanocomposites were obtained from polylactic acid (PLA) and cellulose nanofibers with diameters ranging from 11 nm to 44 nm. The influence of treated (with 3-aminopropyltriethoxysilane) and untreated nanofibers on the thermal properties of PLA was investigated in detail using multiple session Differential Scanning Calorimetry (DSC) analysis. The nucleating effect of the cellulose nanofibers was confirmed by all the DSC runs (two melting and two crystallization steps). The morphology of both neat PLA and nanocomposites was explored for the first time using a new powerful AFM technique, Peak Force QNM (Quantitative Mechanical Property Mapping at the Nanoscale), which emphasized the nanolevel characteristics by elastic modulus mapping. QNM analyses showed a better dispersion of the silane treated nanofibers in the matrix as compared to the untreated ones. Moreover, a higher degree of crystallinity was detected in the PLA composites containing untreated nanofibers compared to the composites with treated ones.

Properties of Polymer Composites with Cellulose Microfibrils

Polypropylene-based composites containing 10–30% by weight cellulose microfibrils were studied. Composites with polypropylene and cellulose microfibrils were characterised by MS-coupled simultaneous TGA-DSC and the reinforcing effect of cellulose microfibrils was emphasised by mechanical characterization. Experimental results are discussed in connection with the composite preparation method by mixing and extrusion. The effect of cellulose on the thermal stability and degradation behaviour of the polypropylene matrix is pointed out.

Biocompatible polyhydroxyalkanoates/bacterial cellulose composites: Preparation, characterization, and in vitro evaluation

Biocompatible composites play a critical role as scaffolds in tissue engineering. Novel biocomposites made from poly(3-hydroxybutyrate) (PHB), polyhydroxyalkanoate (PHA) and bacterial cellulose (BC) in different concentrations were prepared by solution casting and their thermal and mechanical behavior as well as biocompatibility was characterized. BC addition increased the thermal stability of the polymer matrix as evidenced by thermogravimetric analysis. The crystallinity of PHB and the crystallization temperature decreased with the addition of BC and PHA, thus increasing the processing window. BC in small concentration determined an increase in the mechanical properties due to a concerted action of PHA and filler. Good cells attachment and proliferation were observed for all the biocomposites. By the addition of PHA (more hydrophobic than the matrix) and various amounts of BC (highly hydrophilic), surface properties and cell attachment can be controlled. Cytocompatibility studies using L929 cell line revealed that this material is suitable for biomedical applications.

Influence of thermal treatment on mechanical and morphological characteristics of polyamide 11/cellulose nanofiber nanocomposites

Nanocomposite films were prepared from polyamide 11 (PA11) and cellulose nanofibers (CN) by melt compounding and compression molding.The impact of thermal treatment on the morphology and mechanical behavior of PA11 and nanocomposite films was studied using dynamic mechanical analysis, tensile tests, X-ray diffraction (XRD), and peak force (PF) QNM technique. Slightly higher storage modulus values were obtained for nanocomposites compared to the matrix before the treatment, but a noticeable increase was observed after the treatment. Although CN addition determined increased tensile strength and modulus both before and after the treatment, the increase was much more significant in the case of treated films. The best mechanical properties were shown by treated PA11 films containing 5 wt% CN, with 40% higher Youngs modulus and with 35% higher tensile strength compared to the matrix. Some of the changes pointed out by static and dynamic mechanical tests were explained by the morphological changes determined by the thermal treatment and emphasized by PFQNM and by the increase of XRD crystallinity. A transition from lamellar stack morphology to one involving spherulites was highlighted by AFM. Thermal treatment has proved a valuable method for improving the mechanical properties of PA11/CN composites.

Recent Advances in 3D Printing of Aliphatic Polyesters

3D printing represents a valuable alternative to traditional processing methods, clearly demonstrated by the promising results obtained in the manufacture of various products, such as scaffolds for regenerative medicine, artificial tissues and organs, electronics, components for the automotive industry, art objects and so on. This revolutionary technique showed unique capabilities for fabricating complex structures, with precisely controlled physical characteristics, facile tunable mechanical properties, biological functionality and easily customizable architecture. In this paper, we provide an overview of the main 3D-printing technologies currently employed in the case of poly (lactic acid) (PLA) and polyhydroxyalkanoates (PHA), two of the most important classes of thermoplastic aliphatic polyesters. Moreover, a short presentation of the main 3D-printing methods is briefly discussed. Both PLA and PHA, in the form of filaments or powder, proved to be suitable for the fabrication of artificial tissue or scaffolds for bone regeneration. The processability of PLA and PHB blends and composites fabricated through different 3D-printing techniques, their final characteristics and targeted applications in bioengineering are thoroughly reviewed.

Medium chain-length polyhydroxyalkanoate copolymer modified by bacterial cellulose for medical devices

Medium chain-length polyhydroxyalkanoates (mPHAs) are flexible elastomeric biopolymers with valuable properties for biomedical applications like artificial arteries and other medical implants. However, an environmentally friendly and high productivity process together with the tuning of the mechanical and biological properties of mPHAs are mandatory for this purpose. Here, for the first time, a melt processing technique was applied for the preparation of bionanocomposites starting from poly(3-hydroxyoctanoate) (PHO) and bacterial cellulose nanofibers (BC). The incorporation of only 3 wt % BC in PHO improved its thermal stability with 25 °C and reinforced it, increasing the Youngs modulus with 76% and the tensile strength with 44%. The percolation threshold calculated with the aspect ratio of the fibers after melt processing was very low and close to 3 wt %. We showed that this bionanocomposite is able to preserve the ductile behavior during storage, no important aging being noted between 3 h and one month after compression-molding. Moreover, this study is the first to investigate the melt processability of PHO nanocomposite for tube extrusion. In addition, biocompatibility study showed no proinflammatory immune response and better cell adhesion for PHO/BC nanocomposite with 3 wt % BC and demonstrated the high feasibility of this bionanocomposite for in vivo application of tissue-engineered blood vessels.

Treatment of Nanocellulose by Submerged Liquid Plasma for Surface Functionalization

Tailoring the surface properties of nanocellulose to improve the compatibility of components in polymer nanocomposites is of great interest. In this work, dispersions of nanocellulose in water and acetonitrile were functionalized by submerged plasmas, with the aim of increasing the quality of this reinforcing agent in biopolymer composite materials. Both the morphology and surface chemistry of nanocellulose were influenced by the application of a plasma torch and filamentary jet plasma in a liquid suspension of nanocellulose. Depending on the type of plasma source and gas mixture the surface chemistry was modified by the incorporation of oxygen and nitrogen containing functional groups. The treatment conditions which lead to nanocellulose based polymer nanocomposites with superior mechanical properties were identified. This work provides a new eco-friendly method for the surface functionalization of nanocellulose directly in water suspension, thus overcoming the disadvantages of chemical treatments.

Cellulose defibrillation and functionalization by plasma in liquid treatment

Submerged liquid plasma (SLP) is a new and promising method to modify powder materials. Up to now, this technique has been mostly applied to carbonaceous materials, however, SLP shows great potential as a low-cost and environmental-friendly method to modify cellulose. In this work we demonstrate the modification of microcrystalline cellulose (MCC) by applying the SLP combined with ultrasonication treatments. The plasma generated either in an inert (argon) or reactive (argon: oxygen or argon:nitrogen) gas was used in MCC dispersions in water or acetonitrile:water mixtures. An enhanced defibrillation of MCC has been observed following the application of SLP. Furthermore, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy have been applied to investigate the surface functionalization of MCC with oxygen or nitrogen moieties. Depending on the plasma treatment applied, poly (3-hydroxybutyrate) composites fabricated with the plasma modified cellulose fibers showed better thermal stability and mechanical properties than pristine PHB. This submerged liquid plasma processing method offers a unique approach for the activation of cellulose for defibrillation and functionalization, aiming towards an improved reinforcing ability of biopolymers.