In-Situ Quantitative and Multiscale Structural Study of Starch-Based Biomaterials Immersed in Water.

The behavior upon immersion in water of two types of starchy materials of biomedical relevance, amorphous potato starch and glycerol-plasticized potato starch, is analyzed in depth. Synchrotron X-ray scattering, specifically wide-angle X-ray scattering (WAXS), and magnetic resonance microimaging (MRµI) are used as very precise and nondestructive quantitative methods to monitor water transfers and structure changes in the samples, with refined spatial and kinetics results. The ingress of water in the cylinder-shaped samples can be inferred from both techniques, and from this, a diffusion mechanism is deduced for each sample type. Qualitatively, scattering and imaging give comparable results: plasticized samples are shown to behave close to a Fickian diffusion case, amorphous samples close to a case II. WAXS results also provide an in-depth knowledge of the crystalline structures associated to each step of the water ingress, and these are in turn correlated to water diffusion. To refine these observations, a recrystallized starch sample is also analyzed via WAXS. This study gives better insight into the structure of a material with a huge biomedical potential (as implants, for example), and for such applications, the behavior upon immersion in water is particularly relevant.

Short versus long chain polyelectrolyte multilayers: a direct comparison of self-assembly and structural properties.

Successful layer-by-layer (LbL) growth of short chain (∼30 repeat units per chain) poly(sodium styrene sulfonate) (PSS)-poly(diallyl dimethylammonium chloride) (PDADMAC) multilayers is presented for the first time and compared with the growth of equivalent long chain polyelectrolyte multilayers (PEMs). A detailed study performed by quartz crystal microbalance with dissipation (QCM-D) is carried out and three main processes are identified: (i) initial mass uptake, (ii) adsorption-desorption during layer equilibration and (iii) desorption during rinsing. In contrast to the high stability and strong layer increment of high molecular weight (HMW) PEMs, layer degradation characterizes low molecular weight (LMW) multilayers. In particular, two different instability phenomena are observed: a constant decrease of sensed mass during equilibration after PDADMAC adsorption, and a strong mass loss by salt-free rinsing after PSS adsorption. Yet, an increase of salt concentration leads to much stronger layer growth. First, when the rinsing medium is changed from pure water to 0.1 M NaCl, the mass loss during rinsing is reduced, irrespective of molecular weight. Second, an increase in salt concentration in the LMW PE solutions causes a larger increment during the initial adsorption step, with no effect on the rinsing. Finally, the mechanical properties of the two systems are extracted from the measured frequency and dissipation shifts, as they offer a deeper insight into the multilayer structures depending on chain length and outermost layer. The paper enriches the field of PE assembly by presenting the use of very short PE chains to form multilayers and elucidates the role of preparation conditions to overcome the limitation of layer stability.

Water vapor transport properties of bio-based multilayer materials determined by original and complementary methods.

To enhance PLA gas barrier properties, multilayer designs with highly polar barrier layers, such as nanocelluloses, have shown promising results. However, the properties of these polar layers change with humidity. As a result, we investigated water transport phenomena in PLA films coated with nanometric layers of chitosan and nanocelluloses, utilizing a combination of techniques including dynamic vapor sorption (DVS) and long-term water vapor adsorption-diffusion experiments (back-face measurements) to understand the influence of each layer on the behavior of multilayer films. Surprisingly, nanometric coatings impacted PLA water vapor transport. Chitosan/nanocelluloses layers, representing less than 1 wt.% of the multilayer film, increased the water vapor uptake of the film by 14.6%. The nanometric chitosan coating appeared to have localized effects on PLA structure. Moreover, nanocelluloses coatings displayed varying impacts on sample properties depending on their interactions (hydrogen, ionic bonds) with chitosan. The negatively charged CNF TEMPO coating formed a dense network that demonstrated higher resistance to water sorption and diffusion compared to CNF and CNC coatings. This work also highlights the limitations of conventional water vapor permeability measurements, especially when dealing with materials containing ultrathin nanocelluloses layers. It shows the necessity of considering the synergistic effects between layers to accurately evaluate the transport properties.

Resilient high oxygen barrier multilayer films of nanocellulose and polylactide.

Nanocelluloses are promising high gas barrier materials for biobased food packaging, but they must be protected from water to preserve high performance. The respective O2 barrier properties of different types of nanocelluloses were compared (nanofibers (CNF), oxidized nanofibers (CNF TEMPO) and nanocrystals (CNC)). The oxygen barrier performance for all types of nanocelluloses was similarly high. To protect the nanocellulose films from water, a multilayer material architecture was used with poly(lactide) (PLA) on the outside. To achieve this, a biobased tie layer was developed, using Corona treatment and chitosan. This allowed thin film coating with nanocellulose layers between 60 and 440 nm thickness. AFM images treated with Fast Fourier Transform showed the formation of locally-oriented CNC layers on the film. Coated PLA(CNC) films performed better (3.2 × 10-20 m3.m/m2.s.Pa) than PLA(CNF) and PLA(CNF TEMPO) (1.1 × 10-19 at best), because thicker layers could be obtained. The oxygen barrier properties were constant during successive measurements at 0 % RH, 80 % RH and again at 0 % RH. This shows that PLA is sufficiently shielding nanocelluloses from water uptake to keep high performance in an extended range of RH and opens the way to high oxygen barrier films which are biobased and biodegradable.

Cellulose nanocrystals-starch nanocomposites produced by extrusion: Structure and behavior in physiological conditions.

Different amounts of cellulose nanocrystals (CNCs) were added to glycerol-plasticized thermoplastic starch (TPS) to obtain bio-based nanocomposites. First, nanocomposites are prepared by extrusion and their structure is studied at different scales using WAXS (Wide Angle X-ray Scattering) and solid-state NMR (Nuclear Magnetic Resonance) for local/crystalline organization, AF4 (Asymmetrical Flow Field-Flow Fractionation) for molecular weight and chain length, and SEM (Scanning Electron Microscopy) for the morphology at a larger scale. Then, relevant mechanical properties and behavior in physiological conditions (swelling, enzymatic degradation) are characterized. The results show that the incorporation of cellulose nanocrystals up to 2.5 wt% causes a mechanical reinforcement as determined by DMTA (Dynamic Mechanical Thermal Analysis) and reduces the swelling and the enzymatic degradation of the materials compared to reference TPS. This could be linked to the formation of starch-cellulose hydrogen and hydroxyl bonds. Conversely, above 5 wt% CNC content nanocrystals seem to aggregate which in turn worsens the behavior in physiological conditions.

Multi-scale characterization of thermoplastic starch structure using Second Harmonic Generation imaging and NMR.

Starch granules can be extruded to obtain a thermoplastic material. Thermoplastic starch (TPS) usually requires a significant break down of the starch granular organization to form a continuous polysaccharide matrix. In this work, we extrude potato starch with and without a plasticizer and store samples at high humidity to generate recrystallization. A multi-scale investigation of the microstructure is performed by combining different techniques: WAXS and solid-state NMR to describe macromolecule organization and Second Harmonic Generation (SHG) imaging to provide spatial information. Finally, the ability of the material to swell and remain sound in water is assessed. Glycerol-plasticized samples swell the least despite many granules with native-like structure embedded in the starch matrix. Glycerol limits the fragmentation and melting of the granules and crystallites during extrusion but also reduces the proportion of starch molecules in constrained conformations, enabling the formation of a polymer network that can sustain the penetration of water.

Shape-memory effect in amorphous potato starch: The influence of local orders and paracrystallinity.

In this paper, a detailed characterization of the mechanisms at the origin of the shape-memory effect in amorphous potato starch is presented. Using different treatments (annealing) and preparation methods (hot casting and extrusion), the local structures responsible for the shape-memory were disrupted, as evidenced in the first part of the article detailing the macroscopic properties: mechanical, calorimetric and shape-memory. In the second part the macromolecular scale is investigated using X-rays diffraction and CP-MAS NMR, and thus allows making the link between the structural differences and the macroscopic properties. Finally we discuss the origin of shape-memory in amorphous starch.

Interphase vs confinement in starch-clay bionanocomposites.

Starch-clay bionanocomposites containing 1-10% of natural montmorillonite were elaborated by melt processing in the presence of water. A complex macromolecular dynamics behavior was observed: depending on the clay content, an increase of the glass transition temperature and/or the presence of two overlapped α relaxation peaks were detected. Thanks to a model allowing the prediction of the average interparticle distance, and its comparison with the average size of starch macromolecules, it was possible to associate these phenomena to different populations of macromolecules. In particular, it seems that for high clay content (10%), the slowdown of segmental relaxation due to confinement of the starch macromolecules between the clay tactoïds is the predominant phenomenon. While for lower clay contents (3-5%), a significant modification of chain relaxation seems to occur, due to the formation of an interphase by the starch macromolecules in the vicinity of clay nanoparticles coexisting with the bulk polymer.