Hervé Bizot

Influence of equilibrium relative humidity and plasticizer concentration on the water content and glass transition of starch materials

Abstract Sorption behaviour and calorimetric glass transition were measured on cast starch films plasticized with varying concentrations of different components (glycerol, sorbitol, lactic acid sodium, urea, ethylene glycol, diethylene glycol, PEG 200, glycerol diacetate). Precision analysis showed that the water level in samples conditioned at 57% relative humidity reached a minimum for a plasticizer content of 10–20% (dry basis). Starting from 14.8% of water (dry basis) as measured in the amorphous starch-water system, a minimum of 12.7 to 14.4% can be attained according to the type of plasticizer added. Glass transition, as determined on samples conditioned at a constant relative humidity (57%), depended on the type of plasticizer used, although general behaviour was broadly similar for all components except glycerol diacetate. Casting trials performed with this substance revealed an evident phase separation and Tg of starch did not appear really modified by its presence. For glycerol, sorbitol and lactic acid sodium, glass transition was measured with respect to plasticizer and water content. Couchmans relation was applied, which describes the Tg variation of the monophasic polymer—diluant system. The likelihood of phase separation for a high plasticizer level is considered.

Antiplasticization in starch-glycerol films?

Calorimetric, mechanical, and thermomechanical properties have been measured on starch films with various glycerol/water contents. For calorimetric measurements, a continuous decrease in Tg was observed as glycerol increases from 0 to 25%. Mechanical properties exhibit a minimum of elongation at break for glycerol content ∼ 12%. In slightly hydrated starch films not containing another plasticizer, a β relaxation is detected by DMTA around −68°C. This relaxation is modified by the presence of glycerol, the α relaxation of which appears in the same temperature range. Results are discussed comparing with the well-known antiplasticization effect in synthetic polymers such as PVC and PC. The combination of the plasticizer α mode and the polymer β mode is considered.

New Pickering Emulsions Stabilized by Bacterial Cellulose Nanocrystals

We studied oil in water Pickering emulsions stabilized by cellulose nanocrystals obtained by hydrochloric acid hydrolysis of bacterial cellulose. The resulting solid particles, called bacterial cellulose nanocrystals (BCNs), present an elongated shape and low surface charge density, forming a colloidal suspension in water. The BCNs produced proved to stabilize the hexadecane/water interface, promoting monodispersed oil in water droplets around 4 μm in diameter stable for several months. We characterized the emulsion and visualized the particles at the surface of the droplets by scanning electron microscopy (SEM) and calculated the droplet coverage by varying the BCN concentration in the aqueous phase. A 60% coverage limit has been defined, above which very stable, deformable droplets are obtained. The high stability of the more covered droplets was attributed to the particle irreversible adsorption associated with the formation of a 2D network. Due to the sustainability and low environmental impact of cellulose, the BCN based emulsions open opportunities for the development of environmentally friendly new materials.

Modulation of Cellulose Nanocrystals Amphiphilic Properties to Stabilize Oil/Water Interface

Neutral cellulose nanocrystals dispersed in water were shown in a previous work to stabilize oil/water interfaces and produce Pickering emulsions with outstanding stability, whereas sulfated nanocrystals obtained from cotton did not show interfacial properties. To develop a better understanding of the stabilization mechanism, amphiphilic properties of the nanocrystals were modulated by tuning the surface charge density to investigate emulsifying capability on two sources of cellulose: cotton linters (CCN) and bacterial cellulose (BCN). This charge adjustment made it possible to determine the conditions where a low surface charge density, below 0.03 e/nm(2), remains compatible with emulsification, as well as when assisted by charge screening regardless of the source. This study discusses this ability to stabilize oil-in-water emulsions for cellulose nanocrystals varying in crystalline allomorph, morphology, and hydrolysis processes related to the amphiphilic character of nonhydrophobized cellulose nanocrystal.

Calorimetric evaluation of the glass transition in hydrated, linear and branched polyanhydroglucose compounds

By comparing glass transition temperatures, Tg, determined by differential scanning calorimetry (midpoint of heat capacity step at 3 °C.mn−1) on powders of varying water contents for different polysaccharides, the influence of molecular weight, degree of branching and (1–4) vs (1–6) glycosidic linkage ratio upon the depression of Tg is illustrated, thus extending results of former studies. Due to both of the doubts concerning the heat capacity change of water at its glass transition, when dispersed in such media, and limitations of second-order entropy-based derivations, the effect of water plasticization is described by the Couchmans correlation in its degenerated form, which is similar to the Gordon-Taylor formulation. Strong enthalpy relaxation effects are observed following aging treatments at temperatures below, and even far below Tg. This makes it necessary to erase the history of moisture-conditioned samples and, thus, only the second DSC scan results are presented. As expected, linear chains appear to favor chain-chain interactions and induce partial crystallinity; branched molecules display lower Tg values, due to chain end effects, as well as flexibility of branching points. The three dihedrals present in α(1–6) linkages seem to depress Tg in a similar fashion to internal plasticization. The case of a linear α(1–4) amylose chain bearing (1–6) grafted fructoses is examined as a first step towards tailored structures, designed to optimize mechanical properties and internal plasticization (as for chemically modified polysaccharides) and inhibit recrystallization. The extension to ciliated structures (sparse brushes) is proposed as a target for biosynthesis optimization.

Cellulosic nanorods of various aspect ratios for oil in water Pickering emulsions

Cellulosic colloidal nanorods of different origins were used in order to investigate the effect of various elongated shapes adsorbed at the oil–water interface for Pickering emulsion characteristics. Nanocrystals of length ranging from 185 nm to 4 μm were obtained from the hydrolysis of cellulose microfibrils of three different biological origins: cotton (CCN), bacterial cellulose (BCN) and Cladophora (ClaCN) leading to aspect ratios ranging from 13 to 160. These nanocrystals are irreversibly adsorbed at the oil–water interface and form ultrastable emulsions. Individual droplets of similar diameter were obtained under diluted conditions, illustrating both similar wetting properties and nanocrystal flexibility for the three different types of nanocrystals. However, it was shown that the aspect ratio directly influences the coverage ratio giving rise, on the one hand to a dense organisation (coverage >80%) with short nanocrystals and on the other hand to an interconnected network of low covered droplets (40%) when longer nanocrystals are used. An estimation is made showing that for the longer nanocrystals, 55% of the nanocrystals introduced are involved in the network of the material. The capillary force that promotes attractive interactions between nanocrystals was also addressed. These results lead to a better understanding of the adsorption process for rod-like particles of various aspect ratios for the elaboration of a controlled surface architecture, from a homogeneous monolayer to interconnected porous multilayered interfaces.

Crystallinity and structuring role of water in native and recrystallized starches by 13C CP-MAS NMR spectroscopy 1 : Spectral decomposition

Abstract Amorphous, native, and recrystallized starches were studied by 13 C CP-MAS NMR spectroscopy with respect to their behavior with hydration. The study of space groups, associated to crystalline polymorphs (B2 and P6 1 for A and B forms, respectively), provided decomposition rules for the spectral part due to crystalline phases. Moreover, the subtraction of a standard amorphous spectrum apparently showed the existence of three phases in native starches (amorphous, partially-ordered and crystalline) and only two in spherulitic crystals (partially-ordered and crystalline). The proportion of each phase was estimated at two different hydration levels. The amount of crystalline phase was compared to the degree of crystallinity as evaluated by wide angle X-ray scattering. The NMR spectral changes with hydration could be interpreted in terms of two complementary roles of water molecules, i.e. structuring and plasticizing.

Monitoring the crystallization of amylose–lipid complexes during maize starch melting by synchrotron x-ray diffraction

Most starch granules exhibit a natural crystallinity, with different diffraction patterns according to their botanical origin: A-type from cereals and B-type from tubers. The V polymorph results essentially from the complexing of amylose with compounds such as iodine, alcohols, or lipids. The intensity and nature of phase transitions (annealing, melting, polymorphic transitions, recrystallization, etc.) induced by hydrothermal treatments in crystalline structures are related to temperature and water content. Despite its small concentration, the lipid phase present mainly in cereal starches has a large influence on starch properties, particularly in complexing amylose. The formation of Vh crystalline structures was observed by synchrotron x-ray diffraction in native maize starch heated at intermediate and high moisture contents (between 19 and 80%). For the first time, the crystallization of amylose–lipid complexes was evidenced in situ by x-ray diffraction without any preliminary cooling, at heating rates corresponding to the usual conditions for differential scanning calorimetry experiments. For higher water contents, the crystallization of Vh complexes clearly occurred at 110–115°C. For intermediate water contents, mixed A + Vh (or B + Vh for high amylose starch) diffraction diagrams were recorded. Two mechanisms can be involved in amylose complexing: the first relating to crystallization of the amylose and lipid released during starch gelatinization, and the second to crystalline packing of separate complexed amylose chains (amorphous complexes) present in native cereal starches.

Thermal transitions of cassava starch at intermediate water contents

Order-disorder transitions were investigated in native cassava starch at intermediate moisture contents (35 to 60% wt. water), using Differential Scanning Calorimetry (DSC) and dynamic Wide Angle X-ray Diffractometry (WAXS) with a synchrotron radiation source.The gelatinization of granules occurs as a cooperative process, due to constraints induced in crystallites by the amorphous areas. Variations of water content (water volume fraction from 0.28 to 0.86) and heating rate (0.2–10‡C min−1) allowed access to equilibrium melting conditions. Cassava starch exhibits a higher melting temperature of the undiluted starch (Tmo) and an equivalent melting enthalpy of the repeating glucosyl unit (δHu), compared to other A-type starches. At intermediate water content (45% wt. water), a two-stage melting process is evidenced, with different kinetic rates below and above 75 ‡C.

Enthalpic Studies of Xyloglucan−Cellulose Interactions

We report a study of xyloglucan (XG)-cellulose interactions made possible by the preparation of various well-defined cellulosic and xyloglucosidic substrates. Bacterial microcrystalline cellulose (BMCC) as well as cellulose whiskers (CellWhisk) were used as cellulosic substrates. Xyloglucosidic substrates were obtained from Rubus cells and Tamarindus indica seeds. Different primary structure characteristics of XGs such as the backbone length and the nature of the side chains, as well as their repartition, were considered in order to examine the influence of the primary structure on their interaction capacity. Two complementary approaches were carried out: first, the determination of adsorption isotherms and its associated models, and second, an enthalpic study using isothermal titration calorimetry (ITC). This study highlighted that an increase of XG interaction capacity occurred with increasing XG molecular weight. Furthermore, we determined that a minimum of 12 glucosyl residues on the backbone is required to observe significant interactions. Moreover, both the presence of trisaccharidic side chains with fucosyl residues and an increase of unsubstituted glucosyl residues enhanced XG-cellulose interactions. The evolution of adsorption isotherms with temperature and ITC measurements showed that two different processes were occurring, one exothermic and one endothermic, respectively. Although the presence of an exothermic interaction mechanism has long been established, the presence of an endothermic interaction mechanism has never been reported.