Inelastic behaviour of cellulose microfibril networks.

Cellulose microfibrils (CMF) are a unique class of shape anisotropic bio-nanomaterials, already finding many applications in diverse fields owing to their advantageous material properties and abundant availability. The rich non-linear mechanical behaviour of CMF networks has been under-studied due to the complex nature of this system, being influenced by many factors such as strong inter-fibril interactions, a heterogeneous microstructure, and process conditions. In this work, we systematically explore the non-linear rheological behaviour of these networks using a CMF model system with controlled process conditions and fibril interactions. The microfibrils were dispersed in dimethyl sulfoxide to minimise the attractive van der Waals interactions and thereby also the network heterogeneity. We show that the networks exhibit a transition with increasing shear stress from a predominantly elastic to a plastic deformation where they undergo softening. We find that the network stiffness and plasticity are dependent on the loading rate. Finally, we observed that the networks regain their original viscoelastic moduli on cessation of shear. These findings form a basis towards understanding and ultimately modelling the mechanics of CMF networks, which is a prerequisite for the rational design of novel bio-based materials.

Microstructure and rheology of microfibril-polymer networks.

By using an adsorbing polymer in combination with mechanical de-agglomeration, the microstructure and rheological properties of networks of microfibrils could be controlled. By the addition of sodium carboxymethyl cellulose during de-agglomeration of networks of bacterial cellulose, the microstructure could be changed from an inhomogeneous network with bundles of microfibrils and voids to a more homogeneous spread and alignment of the particles. As a result the macroscopic rheological properties were altered. Although still elastic and gel-like in nature, the elasticity and viscous behavior of the network as a function of microfibril concentration is altered. The microstructure is thus changed by changing the surface properties of the building blocks leading to a direct influence on the materials macroscopic behavior.

Dispersions of attractive semiflexible fiberlike colloidal particles from bacterial cellulose microfibrils.

We prepared dispersions from bacterial cellulose microfibrils (CMF) of a commercial Nata de Coco source. We used an ultra-high-energy mechanical deagglomeration process that is able to disperse the CMFs from the pellicle in which they are organized in an irregular network. Because of the strong attractions between the CMFs, the dispersion remained highly heterogeneous, consisting of fiber bundles, flocs, and voids spanning tens to hundreds of micrometers depending on concentration. The size of these flocs increased with CMF concentration, the size of the bundles stayed constant, and the size of the voids decreased. The observed percolation threshold in MFC dispersions is lower than the theoretical prediction, which is accounted for by the attractive interactions in the system. Because bacterial cellulose is chemically very pure, it can be used to study the interaction of attractive and highly shape-anisotropic, semiflexible fiberlike colloidal particles.

Stable and temperature-responsive surfactant-free foamulsions with high oil-volume fraction.

There is more than foam: Optical microscopy images (with false colouring, see picture) depicting quick destabilization (within minutes) of foamulsions due to the coalescence of densely-packed oil droplets when heated at higher temperatures (65 °C).

Predicting thickness perception of liquid food products from their non-Newtonian rheology.

The "mouthfeel" of food products is a key factor in our perception of food quality and in our appreciation of food products. Extensive research has been performed on what determines mouthfeel, and how it can be linked to laboratory measurements and eventually predicted. This was mainly done on the basis of simple models that do not accurately take the rheology of the food products into account. Here, we show that the subjectively perceived "thickness" of liquid foods, or the force needed to make the sample flow or deform in the mouth, can be directly related to their non-Newtonian rheology. Measuring the shear-thinning rheology and modeling the squeeze flow between the tongue and the palate in the oral cavity allows to predict how a panel perceives soup "thickness". This is done for various liquid bouillons with viscosities ranging from that of water to low-viscous soups and for high-viscous xanthan gum solutions. Our findings show that our tongues, just like our eyes and ears, are logarithmic measuring instruments in agreement with the Weber-Fechner law that predicts a logarithmic relation between stimulus amplitude and perceived strength. Our results pave the way for more accurate prediction of mouthfeel characteristics of liquid food products.

Composite Gels Containing Whey Protein Fibrils and Bacterial Cellulose Microfibrils.

In this study, we investigated the gelation of WPI fibrils in the presence of bacterial cellulose (BC) microfibrils at pH 2 upon prolonged heating. Rheology and microstructure were investigated as a function of BC microfibril concentration. The presence of BC microfibrils did not influence the gelation dynamics and resulting overall structure of the WPI fibrillar gel. The storage modulus and loss modulus of the mixed WPI-BC microfibril gels increased with increasing BC microfibril concentration, whereas the ratio between loss modulus and storage modulus remained constant. The WPI fibrils and BC microfibrils independently form two coexisting gel networks. Interestingly, near to the BC microfibrils more aligned WPI fibrils seemed to be formed, with individual WPI fibrils clearly distinguishable. The level of alignment of the WPI fibrils seemed to be dependent on the distance between BC microfibrils and WPI fibrils. This also is in line with our observation that with more BC microfibrils present, WPI fibrils are more aligned than in a WPI fibrillar gel without BC microfibrils. The large deformation response of the gels at different BC microfibril concentration and NaCl concentration is mainly influenced by the concentration of NaCl, which affects the WPI fibrillar gel structures, changing form linear fibrillar to a particulate gel. The WPI fibrillar gel yields the dominant contribution to the gel strength.

Mixed gels from whey protein isolate and cellulose microfibrils.

Whey proteins can form different gel structures ranging from fine-stranded to particulate when appropriate conditions are applied. By incorporating polysaccharides, the gelation of WPI can be influenced. We investigated the heat-induced gelation of whey protein isolate (WPI) in the presence of bacterial cellulose (BC) microfibrils at pH 7 at different concentrations of NaCl. Our results showed that WPI and BC microfibrils form a homogeneous dispersion at pH 7. Upon heating, the WPI gel was formed independently in the presence of the BC microfibril gel, resulting in the formation of a composite gel. The gel structure and gelation dynamics of WPI was not influenced by the presence of BC microfibrils. However, the presence of BC microfibrils increased the storage modulus of the WPI gel, with an increase being negligible when the strength of the WPI gel is above a certain value. With an increase of NaCl concentration, the WPI gel structure changes from fine-stranded to a particulate gel, while the BC microfibril gel structure remains unchanged. No macroscopic phase separation could be observed in the WPI-BC microfibril gels. Our results showed that the rheological properties and water holding capacity of the WPI-BC microfibril mixed gels are mainly dominated by the WPI.

Emulsions stabilised by food colloid particles: role of particle adsorption and wettability at the liquid interface.

We study the effect of the particle wettability on the preferred type of emulsion stabilised solely by food colloid particles. We present results obtained with the recently developed gel trapping technique (GTT) for characterisation of wettability and surface structuring of individual food colloid particles adsorbed at air-water and oil-water interfaces. This method allows us to replicate a particle monolayer onto the surface of polydimethylsiloxane (PDMS) without altering the position of the particles. By observing the polymer surface with scanning electron microscopy (SEM), we are able to determine the contact angle of the individual particles at the initial liquid interface. We demonstrate that the GTT can be applied to fat crystal particles, calcium carbonate particles coated with stearic acid and spray-dried soy protein/calcium phosphate particles at air-water and oil-water interfaces. Subsequently, we prepare emulsions of decane and water stabilised by the same food colloid particles and correlate the wettability data obtained for these particles to the preferred type of emulsions they stabilise.