Cross-linking of polysaccharides by metal ions provides polymer gels highly required by industrial applications. In this article, we study the rheological properties and microstructure of solutions of a stiff anionic polysaccharide xanthan cross-linked by chromium (III) ions, and we demonstrate that their properties are highly sensitive to the preparation pH. Stable gels are obtained in a wide range of pH from 2.4 to 7.8. The maximum elastic modulus is observed for the gels made at pH 6.3, and by freeze-fracture transmission electron microscopy it is shown that they are characterized by the most dense network structure. However, out of this pH interval, no gelation is observed. At low pH (< 2.4) it is due to high protonation of carboxylic groups of xanthan preventing their interaction with chromium ions, and to the disappearance of oligomeric ions, which are effective in cross-linking. At high pH (> 7.8) the absence of gelation is caused by the transformation of reactive chromium ions into insoluble chromium hydroxide. At the same time, for the gels initially formed at pH 6.3, subsequent change of pH to strongly acidic (1.4) or basic (8.9) medium does not affect appreciably their properties, meaning that chromium cross-links are stable once they are formed. These observations open a reliable route to produce polysaccharide gels with required mechanical properties in a wide pH range where they initially cannot be prepared. It is also shown that the increase of pH to 6.3 of the initially ungelled solution prepared at pH 1.5 results in gelation. This effect offers a facile way for delayed gelation of polysaccharides, which is especially required by oil industry.

We report a new facile method for the synthesis of prolate cobalt ferrite nanoparticles without additional stabilizers, which involves a co-precipitation reaction of Fe³⁺ and Co²⁺ ions in a static magnetic field. The magnetic field is demonstrated to be a key factor for the 1D growth of cobalt ferrite nanocrystals in the synthesis. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy are applied to characterize the morphology and structure of the obtained nanoparticles. According to TEM, they represent nanorods with a mean length of 25 nm and a diameter of 3.4 nm that have a monocrystalline structure with characteristic plane spacing of 2.9 Å. XRD and Raman spectroscopy confirm the spinel CoFe₂O₄ structure of the nanorods. After aging, the synthesized nanorods exhibit maximum saturation magnetization and coercivity equal to 30 emu/g and 0.3 kOe, respectively. Thus, the suggested method is a simple and “green” way to prepare CoFe₂O₄ nanorods with high aspect ratios and pronounced magnetic properties, which are important for various practical applications, including biomedicine, energy storage, and the preparation of anisotropic magnetic nanocomposites.

Investigations of structure formation in linear and cross-linked polymer systems including one based on xanthan, an exopolysaccharide, attract theoretical and practical interest because of their widespread applications. Freeze-fracture transmission electron microscopy is used to study the structural topology formed in aqueous xanthan solutions and xanthan hydrogels. The data enable us to visualize for the first time an intact structure of xanthan formed in dilute and semidilute solutions at concentrations ranging from 0.002 to 0.5 wt %. In addition to single macromolecules, the dilute xanthan solutions are shown to contain microgels. When the concentration grows to values close to an overlap concentration (C*), a weak gel structure appears, being composed by a continuous 3D network with relatively large meshes. Macromolecular aggregation is observed in the network skeleton when switching to semidilute entangled solutions (>C**); it is accompanied by a compaction of network structure. The cross-linking of polymer chains by polyvalent Cr³⁺ ions gives a network skeleton composed of aggregated macromolecules at lower concentrations (around C*). Macromolecular aggregation in the skeleton of a network polymer structure occurring both in the absence and in presence of Cr³⁺ cations is indicative of a microphase separation into polymer-poor and polymer-rich regions.

For the first time, gels of a polymer cross-linked by two types of ionic cross-links of different energies, namely trivalent chromium (III) ions and divalent iron (II) ions, were prepared. The negatively charged polysaccharide xanthan, a polyelectrolyte of natural origin, was used as a polymer. A study of xanthan gels cross-linked with each cross-linker separately was carried out to identify the optimal concentrations of each cross-linker for the production of a double cross-linked gel. The mechanical properties of hydrogels under oscillatory shear deformations were then studied. It was demonstrated that the simultaneous use of two cross-linkers resulted in a synergistic increase in the elastic modulus (plateau storage modulus) compared to gels cross-linked with each cross-linker separately. For a gel with two types of cross-links, the elastic modulus was 16 Pa. In contrast, for gels cross-linked with either chromium (III) cations or iron (II) cations, the elastic modulus was approximately 0.6 and 0.5 Pa, respectively. The strong effect can be attributed to the different nature of cross-linking between xanthan macromolecules and chromium (III) and iron (II) cations, as well as the different strength of the cross-links formed. The optimal range of pH values was determined in which a synergistic increase in the elastic modulus of gels with two types of cross-links was observed compared to the corresponding gels cross-linked with each cross-linker separately. Consequently, the concurrent utilisation of two cross-linking agents that generate cross-links with disparate energy levels represents an efficacious strategy to improve the tensile strength of polymer hydrogels.