Viscoelastic surfactants (VES) are amphiphilic molecules which self-assemble into long polymer-like aggregates—wormlike micelles. Such micellar chains form an entangled network, imparting high viscosity and viscoelasticity to aqueous solutions. VES are currently attracting great attention as the main components of clean hydraulic fracturing fluids used for enhanced oil recovery (EOR). Fracturing fluids consist of proppant particles suspended in a viscoelastic medium. They are pumped into a wellbore under high pressure to create fractures, through which the oil can flow into the well. Polymer gels have been used most often for fracturing operations; however, VES solutions are advantageous as they usually require no breakers other than reservoir hydrocarbons to be cleaned from the well. Many attempts have recently been made to improve the viscoelastic properties, temperature, and salt resistance of VES fluids to make them a cost-effective alternative to polymer gels. This review aims at describing the novel concepts and advancements in the fundamental science of VES-based fracturing fluids reported in the last few years, which have not yet been widely industrially implemented, but are significant for prospective future applications. Recent achievements, reviewed in this paper, include the use of oligomeric surfactants, surfactant mixtures, hybrid nanoparticle/VES, or polymer/VES fluids. The advantages and limitations of the different VES fluids are discussed. The fundamental reasons for the different ways of improvement of VES performance for fracturing are described.
The main challenge of modern polymer science is to search for ways of further development of polymer civilization, which obviously includes living organisms on the Earth, without harmful consequences for civilization and the planet in its entirety. The review considers approaches to handle the problem of environmental accumulation of plastic waste. Promising trends in the development of polymer technologies, which can significantly reduce the amount of waste produced, are highlighted. Separate Sections address original methods of additive manufacturing technologies, such as the extrusion printing technique to produce multilayer films, 3D printing by using high-temperature polyimide materials, new functional siloxane oligomers and hydrogels for medical uses. Much attention is paid to the development and applications of biodegradable materials in medicine, packaging industry and agriculture. An analysis of the European strategy for plastics and plastic disposal demonstrates that it has a number of limitations due to high energy requirements and changes in Earth's carbon balance. The modern approach to plastic waste management free from these shortcomings is briefly outlined. Bibliography — 1233 references.
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.