Effects of the Amylose/Amylopectin Ratio of Starch on Borax-Crosslinked Hydrogels.

Herein, we simultaneously prepared borax-crosslinked starch-based hydrogels with enhanced mechanical properties and self-healing ability via a simple one-pot method. The focus of this work is to study the effects of the amylose/amylopectin ratio of starch on the grafting reactions and the performance of the resulting borax-crosslinked hydrogels. An increase in the amylose/ amylopectin ratio increased the gel fraction and grafting ratio but decreased the swelling ratio and pore diameter. Compared with hydrogels prepared from low-amylose starches, hydrogels prepared from high-amylose starches showed pronouncedly increased network strength, and the maximum storage modulus increased by 8.54 times because unbranched amylose offered more hydroxyl groups to form dynamic borate ester bonds with borate ions and intermolecular hydrogen bonds, leading to an enhanced crosslink density. In addition, all the hydrogels exhibited a uniformly interconnected network structure. Furthermore, owing to the dynamic borate ester bonds and hydrogen bonds, the hydrogel exhibited excellent recovery behavior under continuous step strain, and it also showed thermal responsiveness.

Biobased Photopolymer Resin for 3D Printing Containing Dynamic Imine Bonds for Fast Reprocessability.

Acrylic photopolymer resins are widely used in stereolithographic 3D printing. However, the growing demand for such thermosetting resins is weighing on global issues such as waste management and fossil fuel consumption. Therefore, there is an increasing demand for reactive components that are biobased and enable recyclability of the resulting thermoset products. In this work, the synthesis of a photo-cross-linkable molecule containing dynamic imine bonds based on biobased vanillin and dimer fatty diamine is described. Using the biobased building blocks, formulations containing reactive diluent and a photoinitiator were prepared. The mixtures could be rapidly cross-linked under UV light, yielding vitrimers. Using digital light processing, 3D-printed parts were prepared, which were rigid, thermally stable, and reprocessed within 5 min at elevated temperature and pressure. The addition of a building block containing a higher concentration of imine bonds accelerated the stress relaxation and improved the mechanical rigidity of the vitrimers. This work will contribute to the development of biobased and recyclable 3D-printed resins to facilitate the transition to a circular economy.

Biobased 2,5-Bis(hydroxymethyl)furan as a Versatile Building Block for Sustainable Polymeric Materials.

Furanic polymers, currently mainly represented by polyethylene 2,5-furandicarboxylate (PEF), also known as polyethylene furanoate, have a fantastic potential to replace fossil-based polymers: for example, polyethylene terephthalate (PET). While 2,5-furandicarboxylic acid (FDCA), a precursor of PEF, and its derived polymers have been studied extensively, 2,5-bis(hydroxymethyl)furan (BHMF) has received relatively little attention so far. Similarly to FDCA, BHMF is a biobased platform chemical derived from renewable sources such as sugars. This review highlights different polymerization techniques for BHMF-based polyesters and addresses BHMF's relative instability during the synthesis of BHMF-derived polymers, including polycarbonates and polyurethanes. Furthermore, the degradability of furanic polyesters is discussed and BHMF's toxicity is briefly elaborated.

Robust Superamphiphilic Membrane with a Closed-Loop Life Cycle.

Oil-spill remediation is an international environmental challenge, and superamphiphilic membranes, as a promising solution, have recently drawn lots of attention. However, the robustness of the conventional membrane design is less satisfying under severe conditions during practical applications. Additionally, it is unavoidable for the membranes to face a series of foulants in their practical working environment, for example, algae and sand. These foulants will block the membrane, which leads to a new economic and environmental problem in terms of waste management at the end of their life. To address the aforementioned challenges, a new generation of superamphiphilic vitrimer epoxy resin membranes (SAVER) to separate oil and water efficiently is reported. Similar to classical epoxy resins, SAVER shows strong mechanical robustness and sustains exposure to aqua regia and sodium hydroxide solutions. Furthermore, the blocked membrane can be easily recovered when contaminated with mixed foulants by using dynamic transesterification reactions in the polymer network. The ease with which biobased SAVER can be manufactured, used, recycled, and re-used without losing value points to new directions in designing a closed-loop superamphiphilic membrane life cycle.

Sustainable Photopolymers in 3D Printing: A Review on Biobased, Biodegradable, and Recyclable Alternatives.

The global market for 3D printing materials has grown exponentially in the last decade. Today, photopolymers claim almost half of the material sales worldwide. The lack of sustainable resins, applicable in vat photopolymerization that can compete with commercial materials, however, limits the widespread adoption of this technology. The development of "green" alternatives is of great importance in order to reduce the environmental impact of additive manufacturing. This paper reviews the recent evolutions in the field of sustainable photopolymers for 3D printing. It highlights the synthesis and application of biobased resin components, such as photocurable monomers and oligomers, as well as reinforcing agents derived from natural resources. In addition, the design of biologically degradable and recyclable thermoset products in vat photopolymerization is discussed. Together, those strategies will promote the accurate and waste-free production of a new generation of 3D materials for a sustainable plastics economy in the near future.

Stereolithographic 3D Printing with Renewable Acrylates.

The accessibility of cost-competitive renewable materials and their application in additive manufacturing is essential for an efficient biobased economy. We demonstrate the rapid prototyping of sustainable resins using a stereolithographic 3D printer. Resin formulation takes place by straightforward mixing of biobased acrylate monomers and oligomers with a photoinitiatior and optical absorber. Resin viscosity is controlled by the monomer to oligomer ratio and is determined as a function of shear rate by a rheometer with parallel plate geometry. A stereolithographic apparatus charged with the biobased resins is employed to produce complex shaped prototypes with high accuracy. The products require a post-treatment, including alcohol rinsing and UV irradiation, to ensure complete curing. The high feature resolution and excellent surface finishing of the prototypes is revealed by scanning electron microscopy.

Biobased Acrylate Photocurable Resin Formulation for Stereolithography 3D Printing.

To facilitate the ongoing transition toward a circular economy, the availability of renewable materials for additive manufacturing becomes increasingly important. Here, we report the successful fabrication of complex shaped prototypes from biobased acrylate photopolymer resins, employing a commercial stereolithography apparatus (SLA) 3D printer. Four distinct resins with a biobased content ranging from 34 to 67% have been developed. All formulations demonstrated adequate viscosity and were readily polymerizable by the UV-laser-based SLA process. Increasing the double-bond concentration within the resin results in stiff and thermally resilient 3D printed products. High-viscosity resins lead to high-resolution prototypes with a complex microarchitecture and excellent surface finishing, comparable to commercial nonrenewable resins. These advances can facilitate the wide application of biobased resins for construction of new sustainable products via stereolithographic 3D printing methods.

Bioinspired Synthesis of Well-Ordered Layered Organic-Inorganic Nanohybrids: Mimicking the Natural Processing of Nacre by Mineralization of Block Copolymer Templates.

The unique mechanical performance of nacre, the pearly internal layer of shells, is highly dependent on its complex morphology. Inspired by the structure of nacre, the fabrication of well-ordered layered inorganic-organic nanohybrids is presented herein. This biomimetic approach includes the use of a block copolymer template, consisting of hydrophobic poly(vinylidene fluoride) (PVDF) lamellae covered with hydrophilic poly(methacrylic acid) (PMAA), to direct silica (SiO2 ) mineralization. The resulting PVDF/PMAA/SiO2 nanohybrid material resembles biogenic nacre with respect to its well-ordered and layered nanostructure, alternating organic-inorganic phases, macromolecular template, and mild processing conditions.

Gyroid nickel nanostructures from diblock copolymer supramolecules.

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template's channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

Poly(vinylidene fluoride)/nickel nanocomposites from semicrystalline block copolymer precursors.

The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical polymerization (ATRP) of styrene. The crystallization of PVDF plays a dominant role in the formation of the block copolymer structure, resulting in a spherulitic superstructure with an internal crystalline-amorphous lamellar nanostructure. The block copolymer promotes the formation of the ferroelectric ß-polymorph of PVDF. Selective etching of the amorphous regions with nitric acid leads to nanoporous PVDF, which functions as a template for the generation of PVDF/Ni nanocomposites. The lamellar nanostructure and the ß-crystalline phase are conserved during the etching procedure and electroless nickel deposition.

Interface segregating fluoralkyl-modified polymers for high-fidelity block copolymer nanoimprint lithography.

Block copolymer (BCP) lithography is a powerful technique to write periodic arrays of nanoscale features into substrates at exceptionally high densities. In order to place these features at will on substrates, nanoimprint offers a deceptively clear path toward high throughput production: nanoimprint molds are reusable, promote graphoepitaxial alignment of BCP microdomains within their topography, and are efficiently aligned with respect to the substrate using interferometry. Unfortunately, when thin films of BCPs are subjected to thermal nanoimprint, there is an overwhelming degree of adhesion at the mold-polymer interface, which compromises the entire process. Here we report the synthesis of additives to mitigate adhesion based on either PS or PDMS with short, interface-active fluoroalkyl chains. When blended with PS-b-PDMS BCPs and subjected to a thermal nanoimprint, fluoroalkyl-modified PS in particular is observed to substantially reduce film adhesion to the mold, resulting in a nearly defect-free nanoimprint. Subsequent lithographic procedures revealed excellent graphoepitaxial alignment of sub-10 nm BCP microdomains, a critical step toward lower-cost, high-throughput nanofabrication.