Vibrational and structural properties of lead-free piezoelectric (1-x)Na0.5Bi0.5TiO3–xCaTiO3 (0 < x < 1.00) solid solutions have been investigated using Raman spectroscopy and X-ray diffraction. Different anomalies were detected and analyzed taking into consideration the phase transition from rhombohedral to orthorhombic phase at room temperature. All Raman bands were interpreted through the variation in the peak positions (frequency) and the corresponding half-widths at half maximum (HWHM) as a function of x. XRD used as a complementary technique to Raman spectroscopy, showed that the rhombohedral – orthorhombic phase transition went gradually through an intermediate phase consisting of a mixture of rhombohedral (R3c) and orthorhombic (Pnma) structures and that the fraction of orthorhombic phase increased with CT composition. The results show that the morphotropic phase boundary (MPB) is located between 0.09 and 0.15.
Native potato starch is an excellent carrier of minerals due to its inherent ion exchange capacity. Mineral enrichment not only changes the nutritional value but also influences starch pasting and swelling properties. Hydrothermal treatments like annealing constitute a straightforward and green way to tune functional properties. Here, novel combinations of mineral enrichment and annealing were studied. Ion exchange was readily achieved by suspending starch in a salt solution at room temperature over 3 h and confirmed by ICP-OES. Annealing at 50 °C for 24 h using demineralized water or salt solutions strongly affected pasting, thermal, and swelling properties. The obtained XRD and DSC results support a more ordered structure with relative crystallinity increasing from initially 41.7% to 44.4% and gelatinization onset temperature increasing from 60.39 to 65.94 J/g. Solid-state NMR spectroscopy revealed no detectable changes after annealing. Total digestible starch content decreased after annealing from 8.89 to 7.86 g/100 g. During both ion exchange at room temperature and annealing, monovalent cations promoted swelling and peak viscosity, and divalent cations suppressed peak viscosity through ionic crosslinking. The presented combination allows fine-tuning of pasting behavior, potentially enabling requirements of respective food applications to be met while offering an alternative to chemically modified starches.
This study provides insights into novel combinations of hydrothermal modifications and mineral enrichment by demonstrating the versatility of this environmentally more benign approach compared to other common chemical starch modifications like crosslinking. Heat-moisture treatment (HMT) (15 % moisture, 100 °C) of native potato starch (NPS) affords granular products that gelatinise at lower temperatures, hold more water as gel, and are more susceptible to enzymatic digestion. Prior mineral enrichment of NPS with sodium, potassium, magnesium and calcium ions yielded significant changes in pasting curves, with monovalent cations increasing peak viscosity, while divalent cations decrease peak viscosity through ionic crosslinking of phosphate groups, allowing further fine tuning of swelling behaviour. Both short and long HMT (4 h and 16 h) triggered partial disruption of crystallinity and an increase in particle size without visible surface damage as evidenced by X-ray diffraction, laser diffraction and scanning electron microscopy. These novel products may find applications where a thickening agent is needed, and high levels of target minerals are desirable like sport nutrition. The viscosity behaviour, available energy and essential minerals may be beneficial to the formulation and nutritional value of energy gels, while adhering to clean-label requirements of today`s food industry.
