Synthesis of bio-polyol-functionalized nanocrystalline celluloses as reactive/reinforcing components in bio-based polyurethane foams by homogeneous environment modification.

Nanocrystalline Cellulose (NCC or CNC) is widely used as a filler in polymer composites due to its high specific strength, tensile modulus, aspect ratio, and sustainability. However, CNC hydrophilicity complicates its dispersion in hydrophobic polymeric matrices giving rise to aggregate structures and thus compromising its reinforcing action. CNC functionalization in a homogeneous environment, through silanization with trichloro(butyl)silane as a coupling agent and subsequent grafting with bio-based polyols, is herein investigated aiming to enhance CNC dispersibility improving the filler-matrix interaction between the hydrophobic PU and hydrophilic CNC. The modified CNCs (m_Ci) have been studied by XRD, SEM, and TGA analyses. The TGA results show that the amount of grafted polyol is strongly influenced by both its molar mass and OH number and the maximum amount of grafted polyol reaches up to 0.32 mmol per grams of functionalized CNC, within the explored conditions. The effect of different concentrations (1-3 wt%) of m_Ci on the physical, morphological, and mechanical properties of the resulting bio-based composite polyurethane foams is evaluated. Composite PU foams present compressive modulus up to 4.81 MPa and strength up to 255 kPa more than five times higher than those reinforced with unmodified CNC or with modified CNC in heterogeneous chemical environment. The improvement of mechanical properties of the examined PU foams, as a consequence of the incorporation of bio-polyols modified CNCs where polyol's OH groups interact with polyurethane precursors, could further broaden the use of these materials in building applications.

The Role of Superabsorbent Polymers and Polymer Composites in Water Resource Treatment and Management.

In the last century, the issue of "water reserves" has become a remarkably strategic topic in modern science and technology. In this context, water resource treatment and management systems are being developed in both agricultural and urban area scenarios. This can be achieved using superabsorbent polymers (SAPs), highly cross-linked hydrogels with three-dimensional, hydrophilic polymer structures capable of absorbing, swelling and retaining huge amounts of aqueous solutions. SAPs are able to respond to several external stimuli, such as temperature, pH, electric field, and solution composition and concentration. They can be used in many areas, from sensor technology to drug delivery, agriculture, firefighting applications, food, and the biomedical industry. In addition, new categories of functional SAP-based materials, mainly superabsorbent polymer composites, can also encapsulate fertilizers to efficiently provide the controlled release of both water and active compounds. Moreover, SAPs have great potential in wastewater treatment for the removal of harmful elements. In this respect, in the following review, the most promising and recent advances in the use of SAPs and composite SAPs as tools for the sustainable management and remediation of water resource are reviewed and discussed by identifying opportunities and drawbacks and highlighting new challenges and aims to inspire the research community.

Efficient recycling pathway of bio-based composite polyurethane foams via sustainable diamine.

Aminolysis is widely recognized as a valuable chemical route for depolymerizing polymeric materials containing ester, amide, or urethane functional groups, including polyurethane foams. Bio-based polyurethane foams, pristine and reinforced with 40 wt% of sustainable fillers, were depolymerized in the presence of bio-derived butane-1,4-diamine, BDA. A process comparison was made using fossil-derived ethane-1,2-diamine, EDA, by varying amine/polyurethane ratio (F/A, 1:1 and 1:0.6). The obtained depolymerized systems were analyzed by FTIR and NMR characterizations to understand the effect of both diamines on the degradation pathway. The use of bio-based BDA seemed to be more effective with respect to conventional EDA, owing to its stronger basicity (and thus higher nucleophilicity), corresponding to faster depolymerization rates. BDA-based depolymerized systems were then employed to prepare second-generation bio-based composite polyurethane foams by partial replacement of isocyanate components (20 wt%). The morphological, mechanical, and thermal conductivity properties of the second-generation polyurethane foams were evaluated. The best performances (σ10 %=71 ± 9 kPa, λ = 0.042 ± 0.015 W∙ m-1 ∙K-1) were attained by employing the lowest F/A ratio (1:0.6); this demonstrates their potential application in different sectors such as packaging or construction, fulfilling the paradigm of the circular economy.

Effect of Different Methods to Synthesize Polyol-Grafted-Cellulose Nanocrystals as Inter-Active Filler in Bio-Based Polyurethane Foams.

Currently, the scientific community has spent a lot of effort in developing "green" and environmentally friendly processes and products, due the contemporary problems connected to pollution and climate change. Cellulose nanocrystals (CNCs) are at the forefront of current research due to their multifunctional characteristics of biocompatibility, high mechanical properties, specific surface area, tunable surface chemistry and renewability. However, despite these many advantages, their inherent hydrophilicity poses a substantial challenge for the application of CNCs as a reinforcing filler in polymers, as it complicates their dispersion in hydrophobic polymeric matrices, such as polyurethane foams, often resulting in aggregate structures that compromise their properties. The manipulation and fine-tuning of the interfacial properties of CNCs is a crucial step to exploit their full potential in the development of new materials. In this respect, starting from an aqueous dispersion of CNCs, two different strategies were used to properly functionalize fillers: (i) freeze drying, solubilization in DMA/LiCl media and subsequent grafting with bio-based polyols; (ii) solvent exchange and subsequent grafting with bio-based polyols. The influence of the two functionalization methods on the chemical and thermal properties of CNCs was examined. In both cases, the role of the two bio-based polyols on filler functionalization was elucidated. Afterwards, the functionalized CNCs were used at 5 wt% to produce bio-based composite polyurethane foams and their effect on the morphological, thermal and mechanical properties was examined. It was found that CNCs modified through freeze drying, solubilization and bio-polyols grafting exhibited remarkably higher thermal stability (i.e., degradation stages > 100 °C) with respect to the unmodified freeze dried-CNCs. In addition, the use of the two grafting bio-polyols influenced the functionalization process, corresponding to different amount of grafted-silane-polyol and leading to different chemico-physical characteristics of the obtained CNCs. This was translated to higher thermal stability as well as improved functional and mechanical performances of the produced bio-based composite PUR foams with respect of the unmodified CNCs-composite ones (the best case attained compressive strength values three times more). Solvent exchange route slightly improved the thermal stability of the obtained CNCs; however; the so-obtained CNCs could not be properly dispersed within the polyurethane matrix, due to filler aggregation.

Chemically Functionalized Cellulose Nanocrystals as Reactive Filler in Bio-Based Polyurethane Foams.

Cellulose Nanocrystals, CNC, opportunely functionalized are proposed as reactive fillers in bio-based flexible polyurethane foams to improve, mainly, their mechanical properties. To overcome the cellulose hydrophilicity, CNC was functionalized on its surface by linking covalently a suitable bio-based polyol to obtain a grafted-CNC. The polyols grafted with CNC will react with the isocyanate in the preparation of the polyurethane foams. An attractive way to introduce functionalities on cellulose surfaces in aqueous media is silane chemistry by using functional trialkoxy silanes, X-Si (OR)3. Here, we report the synthesis of CNC-grafted-biopolyol to be used as a successful reactive filler in bio-based polyurethane foams, PUFs. The alkyl silanes were used as efficient coupling agents for the grafting of CNC and bio-polyols. Four strategies to obtain CNC-grafted-polyol were fine-tuned to use CNC as an active filler in PUFs. The effective grafting of the bio polyol on CNC was evaluated by FTIR analysis, and the amount of grafted polyol by thermogravimetric analysis. Finally, the morphological, thermal and mechanical properties and hydrophobicity of filled PUFs were thoughtfully assessed as well as the structure of the foams and, in particular, of the edges and walls of the cell foams by means of the Gibson-Ashby model. Improved thermal stability and mechanical properties of PU foams containing CNC-functionalized-polyol are observed. The morphology of the PU foams is also influenced by the functionalization of the CNC.

Three-Dimensional Quantitative Intracellular Visualization of Graphene Oxide Nanoparticles by Tomographic Flow Cytometry.

Interaction of nanoparticles (NPs) with cells is of fundamental importance in biology and biomedical sciences. NPs can be taken up by cells, thus interacting with their intracellular elements, modifying the life cycle pathways, and possibly inducing death. Therefore, there is a great interest in understanding and visualizing the process of cellular uptake itself or even secondary effects, for example, toxicity. Nowadays, no method is reported yet in which 3D imaging of NPs distribution can be achieved for suspended cells in flow-cytometry. Here we show that, by means of label-free tomographic flow-cytometry, it is possible to obtain full 3D quantitative spatial distribution of nanographene oxide (nGO) inside each single flowing cell. This can allow the setting of a class of biomarkers that characterize the 3D spatial intracellular deployment of nGO or other NPs clusters, thus opening the route for quantitative descriptions to discover new insights in the realm of NP-cell interactions.

Upgrading Sustainable Polyurethane Foam Based on Greener Polyols: Succinic-Based Polyol and Mannich-Based Polyol.

It is well known that the traditional synthetic polymers, such as Polyurethane foams, require raw materials that are not fully sustainable and are based on oil-feedstocks. For this reason, renewable resources such as biomass, polysaccharides and proteins are still recognized as one of the most promising approaches for substituting oil-based raw materials (mainly polyols). However, polyurethanes from renewable sources exhibit poor physical and functional performances. For this reason, the best technological solution is the production of polyurethane materials obtained through a partial replacement of the oil-based polyurethane precursors. This approach enables a good balance between the need to improve the sustainability of the polymer and the need to achieve suitable performances, to fulfill the technological requirements for specific applications. In this paper, a succinic-based polyol sample (obtained from biomass source) was synthesized, characterized and blended with cardanol-based polyol (Mannich-based polyol) to produce sustainable rigid polyurethane foams in which the oil-based polyol is totally replaced. A suitable amount of catalysts and surfactant, water as blowing reagent and poly-methylene diphenyl di-isocyanate as isocyanate source were used for the polyurethane synthesis. The resulting foams were characterized by means of infrared spectroscopy (FTIR) to control the cross-linking reactions, scanning electron microscopy (SEM) to evaluate the morphological structure and thermal gravimetric analysis (TGA) and thermal conductivity to evaluate thermal degradation behavior and thermal insulation properties.