Mid Sweden University

Chelating surfactants are amphiphilic molecules capable of forming coordination complexes with metal ions and self-assembling into organized structures. These compounds have gained significant attention in recent years due to their multifaceted applications in environmental remediation, industrial processes, and material sciences. This review provides an overview of the characterization techniques and recent advancements in the applications of chelating surfactants over the past few years. The review begins by elucidating the characterization methods employed to understand the physicochemical properties of chelating surfactants and gain insight into their complex behavior and interactions in various systems. The applications of chelating surfactants in remediation of wastewater and soil, flotation of minerals, oil recovery processes, and corrosion inhibition in metallic structures are explored. Through examination of recent fundamental research activities, innovative approaches, mechanisms of action, and advancements in the different application domains are highlighted. Lastly, some recent progress in the related field of metallosurfactants is explored, even though not all metallosurfactants are chelating. 

2-Dodecyldiethylenetriaminepentaacetic acid (C12-DTPA) is a chelating, amphoteric surfactant with a bulky headgroup containing eight pH-responsive groups. The hypothesis was that the amphoteric nature of the chelating surfactant would affect the interaction with another surfactant and, consequently, also the composition of mixed surface layers. Binary mixed monolayers of C12-DTPA and the anionic surfactant sodium dodecyl sulfate (SDS) were examined using neutron reflection and surface tension measurements. The experiments were conducted at pH 5, where the C12-DTPA monomers carried a net negative charge. Surface excess calculations at low total surfactant concentration revealed that the chelating surfactant dominated the surface composition. However, as the concentration was raised, the surface composition shifted toward an SDS-dominant state. This phenomenon was attributed to the increased ionic strength at increased concentrations, which altered the balance between competing entropic forces in the system. Interaction parameters for mixed monolayer formation were calculated, following a framework based on regular solution theory. In accordance with the hypothesis, the chelating surfactant’s ability to modulate its charge and mitigate repulsive interactions in the surface layer resulted in favorable interactions between the anionic SDS and negatively charged C12-DTPA monomers. These interactions were found to be concentration-dependent, which was consistent with the observed shift in the surface layer composition. 

Cellulose laminates represent a remarkable convergence of natural materials and modern engineering, offering a wide range of versatile applications in sustainable packaging, construction, and advanced materials. In this study, novel all-cellulose laminates are developed using an environmentally friendly approach, where freshly regenerated cellulose II films are stacked without the need for solvents (for impregnation and/or partial dissolution), chemical modifications, or resins. The structural and mechanical properties of these all-cellulose laminates were thoroughly investigated. This simple and scalable procedure results in transparent laminates with exceptional mechanical properties comparable to or even superior to common plastics, with E-modulus higher than 9 GPa for a single layer and 7 GPa for the laminates. These laminates are malleable and can be easily patterned. Depending on the number of layers, they can be thin and flexible (with just one layer) or thick and rigid (with three layers). Laminates were also doped with 10 wt% undissolved fibers without compromising their characteristics. These innovative all-cellulose laminates present a robust, eco-friendly alternative to traditional synthetic materials, thus bridging the gap between environmental responsibility and high-performance functionality. 

The demands for alternatives to fossil-based materials for the packaging and building sector is rapidly increasing as new regulations and laws are set. The usage of such materials in low- density applications is increasingly questioned since only a small amount is recycled and a large part ends up in the environment where it has a very long decomposition time and contributes to the emergence of microplastics in our marine eco systems. Alternatives to fossil- based low-density materials has been demonstrated using e.g., starch [1] and cellulose [2] as raw materials. However, challenges remain regarding the process parameters and properties such as strength and water integrity. To fulfil these properties requested by the specification owners, understanding is needed regarding which tools that are available for incorporating wet-integrity and hydrophobicity without causing the wet foam to collapse during the foaming or drying process. It is also of highest importance to have an early understanding of how such materials can be recycled and/or bio-degraded to fit a circular economy. In this study two different cross-linkers and two different types of hydrophobisers are used to obtain a wet stable and a water repelling low-density material. The wet foams are characterized by measuring the foamability and foam stability and the dry foams are characterized in terms of structure, porosity and degradability. Two demonstrators have been produced based on the most promising material composition and the up-scaling processes of the developed foaming technology to both batch-wise and continuous fabrication of composite foams is underway. Finally, a biodegradation study was conducted and evaluated.

[1] S. Chaireh, P. Ngasatool, and K. Kaewtatip, “Novel composite foam made from starch and water hyacinth with beeswax coating for food packaging applications,” Int. J. Biol. Macromol., vol. 165, pp. 1382–1391, 2020

[2] C. Qin, M. Yao, Y. Liu, Y. Yang, Y. Zong, and H. Zhao, “MFC/NFC-based foam/aerogel for production of porous materials: Preparation, properties and applications,” Materials (Basel)., vol. 13, no. 23, pp. 1–21, 2020

Cellulose acetate butyrate (CAB) is a possible candidate, being a raw material derived from renewable resources, to replace fossil-based materials. This is due to its thermoplastic properties and the relative ease with which it could be implemented within the existing industry. With a significant amount of variation in CAB on the market today, a knowledge gap has been identified regarding the understanding of the polymer structural arrangement in films. This relates to the underlying mechanisms that regulate CAB film material properties, insights that are important in product development. In this study, commercially available CAB was investigated with XRD, SEM, AFM, and TOPEM DSC in order to obtain physicochemical information related to its micro-structural features in solvent-cast films. The film-forming ability relates mostly to the number of hydroxyl groups, and the semi-crystallinity of the films depends on the type and position of the side groups along the cellulose backbone. The appearance of signs of possible cholesteric ordering in the films could be connected to higher amounts of hydroxyl groups along the backbone that disturb the helix arrangement, while the overall order was primarily related to the butyrate substitution and secondarily related to the molecular weight of the particular CAB studied. Cold crystallization was also observed in one CAB sample.

In the history of cellulose chemistry, hydrogen bonding has been the predominant explanation when discussing intermolecular interactions between cellulose polymers. This is the general consensus in scholarly textbooks and in many research articles, and it applies to several other biomacromolecules’ interactions as well. This rather unbalanced description of cellulose has likely impacted the development of materials based on the processing of cellulose—for example, via dissolution in various solvent systems and regeneration into solid materials, such as films and fibers, and even traditional wood fiber handling and papermaking. In this review, we take as a starting point the questioning of the general description of the nature of cellulose and cellulose interactions initiated by Professor Björn Lindman, based on generic physicochemical reasoning about surfactants and polymers. This dispute, which became known as “the Lindman hypothesis”, highlights the importance of hydrophobic interactions in cellulose systems and that cellulose is an amphiphilic polymer. This paper elaborates on Björn Lindman’s contribution to the subject, which has caused the scientific community to revisit cellulose and reconsider certain phenomena from other perspectives. 

With amphiphilic properties, cellulose molecules are expected to adsorb at the O/W interface and be capable of stabilizing emulsions. The effect of solvent quality on the formation and stability of cellulose-based O/W emulsions was evaluated in different alkaline systems: NaOH, NaOH-urea and tetrabutylammonium hydroxide (TBAH). The optimal solvency conditions for cellulose adsorption at the O/W interface were found for the alkaline solvent with an intermediate polarity (NaOH-urea), which is in line with the favorable conditions for adsorption of an amphiphilic polymer. A very good solvency (in TBAH) and the interfacial activity of the cation lead to lack of stability because of low cellulose adsorption. However, to achieve long-term stability and prevent oil separation in NaOH-urea systems, further reduction in cellulose's solvency was needed, which was achieved by a change in the pH of the emulsions, inducing the regeneration of cellulose at the surface of the oil droplets (in-situ regeneration).

Aqueous sodium hydroxide solutions are extensively used as solvents for lignin in kraft pulping. These are also appealing systems for cellulose dissolution due to their inexpensiveness, ease to recycle and low toxicity. Cellulose dissolution occurs in a narrow concentration region and at low temperatures. Dissolution is often incomplete but additives, such as zinc oxide or urea, have been found to significantly improve cellulose dissolution. In this work, lignin was explored as a possible beneficial additive for cellulose dissolution. Lignin was found to improve cellulose dissolution in cold alkali, extending the NaOH concentration range to lower values. The regenerated cellulose material from the NaOH-lignin solvents was found to have a lower crystallinity and crystallite size than the samples prepared in the neat NaOH and NaOH-urea solvents. Beneficial lignin-cellulose interactions in solution state appear to be preserved under coagulation and regeneration, reducing the tendency of crystallization of cellulose. 

In this study, the effect of different alcohols and esters as a coagulation medium in the regeneration of cellulose dissolved in an aqueous LiOH-urea-based solvent was thoroughly investigated using various methods such as solid state NMR, X-ray diffraction, water contact angle, oxygen gas permeability, mechanical testing, and scanning electron microscopy. It was observed that several material properties of the regenerated cellulose films follow trends that correlate to the degree of cellulose II crystallinity, which is determined to be set by the miscibility of the coagulant medium (nonsolvent) and the aqueous alkali cellulose solvent rather than the nonsolvents’ polarity. This article provides an insight, thus creating a possibility to carefully tune and control the cellulose material properties when tailor-made for different applications. 

Lignocellulose biomass plays an important role in reducing thedependency on fossil fuels and ameliorating the dire consequences ofclimate change. It is therefore important that all the components oflignocellulose biomass are exploited. These components includehemicelluloses and extractives that are liberated and sterically stabilizedduring the thermomechanical pulping and that form the dissolved andcolloidal substance (DCS) in the process water. Biorefining of this processwater can extract these substances, which have a number of promisingapplications and can contribute to the full exploitation of lignocellulosebiomass. This paper presents a simple treatment of unbleached Norwayspruce (Picea abies) process water from TMP (thermomechanical pulping)production using induced air flotation (IAF) and cationic surfactant,dodecyl trimethylammonium chloride (DoTAC) to refine the extractivesand prepare the waters so that hemicellulose could be easily harvested ata later stage. By applying 80 ppm of DoTAC at a pH of 3.5 and 50 °Cbefore induced air flotation, 94% of the lipophilic extractives wererecovered from process water. Dissolved hemicellulose polysaccharideswere cleansed and left in the treated process water. The process enabledefficient biorefining of lipophilic extractives and purification of the processwater to enable more selective harvesting of hemicelluloses in subsequentsteps.