Pronounced fibres are formed through simple shearing of a dense calcium caseinate dispersion. Both mechanical tests and scanning electron microscopy images demonstrate that the material is anisotropic. It is hypothesised that calcium caseinate aggregates, under shear, align into micro-fibres and bundle further into a hierarchical structure. Yet no direct evidence at the sub-micron length scale can support the assumption. Small angle neutron scattering (SANS) experiments were conducted on calcium caseinate samples prepared at different conditions. Analysis of the SANS data revealed that the micro-fibres have a diameter of ∼100nm and a length of ∼300nm. The addition of enzyme and air contributed to longer and thinner micro-fibres. Furthermore, the extent of fibre alignment at the micro-scale and the macroscopic anisotropy index followed the same trends with varying processing conditions. It is concluded that the material does indeed possess a hierarchical structure and the micro-fibres are responsible for the anisotropy on the macro-scale.

Dense calcium caseinate dispersions can be transformed into hierarchically fibrous structures by shear deformation. This transformation can be attributed to the intrinsic properties of calcium caseinate. Depending on the dispersion preparation method, a certain amount of air gets entrapped in the sheared protein matrix. Although anisotropy is obtained in the absence of entrapped air, the fibrous appearance and mechanical anisotropy of the calcium caseinate materials are more pronounced with dispersed air present. The presence of air induces the protein fibers to be arranged in microscale bundles, and the fracture strain and stress in the parallel direction are larger compared with the material without air. The effects can be understood from the alignment of the fibers in the parallel direction, providing strain energy dissipation. This study shows that creation of anisotropy is the result of interactions between multiple phases.

Calcium caseinate dispersions can be transformed into anisotropic, fibrous materials using the concept of shear-induced structuring. The aim of this study is to further investigate the relative importance of air bubbles and protein on the mechanical anisotropy of calcium caseinate material. In this study, the effect of air on mechanical anisotropy of these fibrous materials was described with a load-bearing model, with the void fraction, and the bubble length and width as input parameters. The anisotropy of the protein phase was estimated using materials obtained from deaerated dispersions after shearing at different shear rates. We concluded that the deformation of air bubbles can only partly explain the mechanical anisotropy; the anisotropy of the protein phase is more important. Based on all results, we further concluded that the anisotropy of the protein phase was affected by the air bubbles present during the structuring process. This effect was explained by locally higher shear rate in the protein matrix during the structuring process.