Fully biobased hydrogel based on chitosan and tannic acid coated cotton fabric for underwater superoleophobicity and efficient oil/water separation.

Underwater superoleophobic (UWSO) materials have garnered significant attention in separating oil/water mixtures. But, the majority of these materials are made from non-degradable and non-renewable raw materials, polluting the environment and wasting scarce resources while using them. Against this backdrop, this study aimed to fabricate an environmental-friendly UWSO textile using biobased materials. To achieve this, hydrogel consisting of chitosan (CS) and poly(tannic acid) (PTA) were formed and coated on cotton fabric (CTF) via dip-coating followed by oxidative polymerization. CS&PTA hydrogel endowed the CTF with a rough surface and high surface energy, leading to an UWSO CTF with an underwater oil contact angle as high as 166.84°. The CS&PTA/CTF had excellent separation capability toward various oil/water mixtures, showing separation efficiency above 99.84 % and water flux higher than 23, 999 L m-2 h-1. Moreover, CS&PTA/CTF possessed excellent mechanical and environmental stability with underwater superoleophobicity unchanged after sandpaper friction, ultrasonication, organic solvents, NaCl (m/v, 30 %) solution, and acid/base solution immersion, due to the strong interaction between the hydrogel and cotton fabric generated by the mussel-inspired adhesion owing to the presence of PTA. The fully biobased UWSO CTF exhibits great promising to be an alternative to traditional superwetting materials for separation of oil/water mixtures.

Fabrication of well-dispersed cellulose nanocrystal reinforced biobased epoxy composites using reversibility of covalent adaptable network.

Cellulose nanocrystal (CNC) shows great potential in reinforced composites but it is difficult to disperse in epoxy thermosets due to its poor dispersity in epoxy monomers. Herein, we reported a novel approach to disperse CNC in epoxidized soybean oil (ESO)-derived epoxy thermosets uniformly by using the reversibility of dynamic imine-containing ESO-derived covalent adaptable network (CAN). The crosslinked CAN was deconstructed by an exchange reaction with ethylenediamine (EDA) in dimethyl formamide (DMF), leading to a solution of deconstructed CAN with plenty of hydroxyl and amino groups, which could form strong hydrogen bonds with hydroxyl groups of CNC and thus facilitated and stabilized dispersion of CNC in the deconstructed CAN solution. Epoxy composite with well-dispersed CNC was finally achieved by a reformation of CAN through the removal of DMF and EDA. In this way, the epoxy composites with CNC content up to 30 wt% were successfully prepared and showed drastically reinforced mechanical properties. The tensile strength and Young's modulus of the CAN were improved by up to ∼70 % and ∼45 times with the incorporation of 20 and 30 wt% CNC, respectively. The composites showed excellent reprocessability without significant loss in mechanical properties after reprocessing.

Fully biobased poly(lactic acid)/lignin composites compatibilized by epoxidized natural rubber.

Biobased poly(lactic acid)/lignin (PLA/lignin) composites are limited by poor mechanical properties resulted from poor compatibility and low interfacial adhesion. Herein, we reported a novel approach to improve compatibility and interfacial adhesion of PLA/lignin composites via reactive compatibilization with epoxidized natural rubber (ENR) as a compatibilizer. Interfacial tension calculation indicated that lignin tended to act as interfacial phase between PLA and ENR, but morphology analysis demonstrated lignin was wrapped with a layer of ENR and dispersed in PLA matrix, which was attributed to the interfacial reaction of ENR with both PLA and lignin. The interfacial reaction was confirmed by Fourier transform infrared spectroscopy. The compatibility and interfacial adhesion between PLA and lignin were improved significantly by incorporation and increase in the content of ENR, as evidenced by the reduced interfacial gaps, blurry phase boundaries, and enhanced elastic response. As such, the mechanical properties of PLA/lignin composites were enhanced significantly. The tensile strength and elongation at break of PLA/lignin (W/W, 80/20) were improved by 15 % and 77 %, respectively, with the incorporation of only 1 wt% ENR. We believe this approach to compatibilize PLA/lignin composites is promising because it would not require costly modification of lignin and would not compromise the sustainability of composites.

Biobased mussel-inspired underwater superoleophobic chitosan derived complex hydrogel coated cotton fabric for oil/water separation.

Superhydrophilic and underwater superoleophobic materials exhibit excellent oil/water separation performance but are usually fabricated from nonrenewable and nondegradable feedstocks and thus would cause secondary pollution after use. Herein, we report a fully biobased and mussel-inspired underwater superoleophobic hydrogel coated cotton fabric (CF) prepared by surface coating and subsequent oxidation polymerization of chitosan & dopamine mixtures. The obtained chitosan & polydopamine hydrogel coated CF (CS&PDA/CF) showed superhydrophilicity and underwater superoleophobicity, due to the formed rough surface structure with hydrophilic complex hydrogel. The CS&PDA/CF exhibited excellent oil/water separation performance with separation efficiency higher than 99.5% for various oil/water mixtures. Moreover, the CS&PDA/CF showed excellent resistance against various harsh conditions such as boiling water, ultrasonication, and concentrated salt solution, due to the mussel-inspired strong adhesion stabilized structure and morphology. We believe that the fully biobased and mussel-inspired underwater superoleophobic cotton fabric shows great potential as an eco-friendly and high-efficient oil/water separation material.

Dynamic Crosslinking: An Efficient Approach to Fabricate Epoxy Vitrimer.

Epoxy vitrimers with reprocessability, recyclability, and a self-healing performance have attracted increasingly attention, but are usually fabricated through static curing procedures with a low production efficiency. Herein, we report a new approach to fabricate an epoxy vitrimer by dynamic crosslinking in a torque rheometer, using diglycidyl ether of bisphenol A and sebacic acid as the epoxy resin and curing agent, respectively, in the presence of zinc acetylacetonate as the transesterification catalyst. The optimal condition for fabricating the epoxy vitrimer (EVD) was dynamic crosslinking at 180 °C for ~11 min. A control epoxy vitrimer (EVS) was prepared by static curing at 180 °C for ~11 min. The structure, properties, and stress relaxation of the EVD and EVS were comparatively investigated in detail. The EVS did not cure completely during static curing, as evidenced by the continuously increasing gel fraction when subjected to compression molding. The gel fraction of the EVD did not change with compression molding at the same condition. The physical, mechanical, and stress relaxation properties of the EVD prepared by dynamic crosslinking were comparable to those of the EVS fabricated by static curing, despite small differences in the specific property parameters. This study demonstrated that dynamic crosslinking provides a new technique to efficiently fabricate an epoxy vitrimer.

Mussel-inspired chitosan modified superhydrophilic and underwater superoleophobic cotton fabric for efficient oil/water separation.

Superhydrophilic and underwater superoleophobic textiles exhibit excellent oil/water separation performance but are limited by the poor stability and environmental incompatibility. Inspired by strong adhesion of marine mussels, we designed and fabricated a stable and eco-friendly superhydrophilic and underwater superoleophobic cotton fabric (CF) from all renewable resources through in-situ surface deposition of polydopamine (PDA) particles followed by adsorption of hydrophilic chitosan via dip coating at room temperature. The as-prepared superhydrophilic and underwater superoleophobic CF exhibited outstanding oil/water separation performance with separation efficiency and water flux higher than 99 % and 15,000 L m-2 h-1, respectively. Moreover, it not only showed excellent resistance to mechanical abrasion and ultrasound treatment but also had outstanding superwetting stability against acid/alkali/salt erosion. We believed that the eco-friendly superhydrophilic and underwater superoleophobic CF would exhibit great potential in oil/water separation especially under harsh conditions.

Robust and nanoparticle-free superhydrophobic cotton fabric fabricated from all biological resources for oil/water separation.

Traditional superhydrophobic cotton fabrics (SCFs) for oil/water separation were usually fabricated by surface coating with inorganic nanoparticles combined with nonrenewable and nonbiodegradable or even toxic fossil-based chemicals, which would lead to secondary environmental pollution after their lifetime. In this study, we report robust, nanoparticle-free, fluorine-free SFC, which was prepared by acid etching followed by surface coating with epoxidized soybean oil resin (CESO) and subsequent modification with stearic acid (STA). No toxic compound and no nanoparticle were included within the SCF and all the raw materials including cotton fabric, CESO and STA are biodegradable and derived from biological resources. The SCF showed excellent mechanical stability and chemical/environmental resistances. The superhydrophobicity of the SFC survived from mechanical abrasion, tape peeling, ultrasonication, solvent erosion and low/high temperature exposure. The SCF also exhibited good acid/alkali resistance with contact angle over 150° toward different pH water droplets. Moreover, the SCF could efficiently separate oil/water mixtures with efficiency above 97.9% and the superhydrophobicity remained after reusing for at least 10 times. The fully biological-derived SCF with excellent mechanical and chemical resistances exhibit great potential for separation of oil/water mixtures.

Cellulose nanocrystal coated cotton fabric with superhydrophobicity for efficient oil/water separation.

Cellulose nanocrystal (CNC) with renewability, biodegradability, and nanoscale size was used as the rough structure component instead of inorganic nanoparticles to fabricate renewable and degradable superhydrophobic cotton fabric via a dip-coating method with cured epoxidized oil resin (CESO) as the binder. The superhydrophobic cotton fabric could selectively absorb oil from oily water and could separate various oil/water mixture very efficiently with separation efficiency higher than 98%. The superhydrophobic cotton fabric showed excellent stability, making it reusable for several times without lowering separation efficiency. Moreover, the superhydrophobic cotton fabric exhibited excellent solvent and chemical resistances. Furthermore, the superhydrophobic cellulosic fabric was degradable with weight loss of 14.4 wt% after hydrolytic degradation in phosphate buffer solution (pH 7.4) at 37 °C for 10 weeks. The superhydrophobic cotton fabric may exhibit great viability as sustainable and degradable alternative to traditional nonrenewable and non-degradable superhydrophobic materials in oil/water separation.

Enhanced electrical conductivity and piezoresistive sensing in multi-wall carbon nanotubes/polydimethylsiloxane nanocomposites via the construction of a self-segregated structure.

Formation of highly conductive networks is essential for achieving flexible conductive polymer composites (CPCs) with high force sensitivity and high electrical conductivity. In this study, self-segregated structures were constructed in polydimethylsiloxane/multi-wall carbon nanotube (PDMS/MWCNT) nanocomposites, which then exhibited high piezoresistive sensitivity and low percolation threshold without sacrificing their mechanical properties. First, PDMS was cured and pulverized into 40-60 mesh-sized particles (with the size range of 250-425 µm) as an optimum self-segregated phase to improve the subsequent electrical conductivity. Then, the uncured PDMS/MWCNT base together with the curing agent was mixed with the abovementioned PDMS particles, serving as the segregated phase. Finally, the mixture was cured again to form the PDMS/MWCNT nanocomposites with self-segregated structures. The morphological evaluation indicated that MWCNTs were located in the second cured three-dimensional (3D) continuous PDMS phase, resulting in an ultralow percolation threshold of 0.003 vol% MWCNTs. The nanocomposites with self-segregated structures with 0.2 vol% MWCNTs achieved a high electrical conductivity of 0.003 S m-1, whereas only 4.87 × 10-10 S m-1 was achieved for the conventional samples with 0.2 vol% MWCNTs. The gauge factor GF of the self-segregated samples was 7.4-fold that of the conventional samples at 30% compression strain. Furthermore, the self-segregated samples also showed higher compression modulus and strength as compared to the conventional samples. These enhanced properties were attributed to the construction of 3D self-segregated structures, concentrated distribution of MWCNTs, and strong interfacial interaction between the segregated phase and the continuous phase with chemical bonds formed during the second curing process. These self-segregated structures provide a new insight into the fabrication of elastomers with high electrical conductivity and piezoresistive sensitivity for flexible force-sensitive materials.

Morphology, crystallization and rheological behavior in poly(butylene succinate)/cellulose nanocrystal nanocomposites fabricated by solution coagulation.

Nanocomposites consisting of poly(butylene succinate) (PBS) and cellulose nanocrystals (CNC) were fabricated by solution coagulation method. Morphology analysis indicated that CNC dispersed well in PBS matrix and rheological analysis suggested that PBS and CNC showed strong interactions. Thermal analysis indicated that the nanocomposites showed slightly increased glass transition temperature, significantly enhanced crystallization temperature and different melting behavior, compared to neat PBS. Study on crystallization indicated that small loading of CNC could significantly increase overall crystallization rate of PBS, meanwhile the crystallization mechanism and crystal structure remained unchanged. The significant enhancement in overall crystallization was attributed to the increased nucleation ability by incorporation of well dispersed CNC nanoparticles. Tensile testing indicated that the tensile strength and modulus were gradually improved with increasing CNC content, while the elongation at break decreased and even brittle fracture occurred when the content of CNC increased to 1.0wt%.

Control of the Crystalline Morphology of Poly(l-lactide) by Addition of High-Melting-Point Poly(l-lactide) and Its Effect on the Distribution of Multiwalled Carbon Nanotubes.

The key to fabricating conductive polymer/carbon nanotube (CNT) nanocomposites is controlling the distribution of CNTs in the polymer matrix. Here, an effective and simple approach for controlling the distribution of multiwalled CNTs (MWCNTs) is reported to largely improve the electrical conductivity of biodegradable poly(l-lactide) (PLLA) through crystalline morphology development by addition of high-melting-point PLLA (hPLLA) crystallites. hPLLA crystallites are efficient nucleating agents, increasing the crystallinity and crystallization rate of PLLA/MWCNT nanocomposites. Furthermore, the diameter of spherulites decreases from 9.7 to 1.0 µm with an increase in the concentration of hPLLA from 0.03 to 3.0 wt %. The electrical conductivity of PLLA/MWCNT nanocomposites with 0.3 wt % MWCNTs greatly increases from 1.89 × 10(-15) to 1.56 × 10(-8) S/cm with an increase in the matrix crystallinity from 2.4 to 46.8% on introducing trace amounts of hPLLA (0.07 wt %). The percolation threshold of PLLA/MWCNT nanocomposites is reduced from 0.51 to 0.21 wt % on addition of 0.07 wt % hPLLA. The high electrical conductivity and low percolation threshold of PLLA/MWCNT nanocomposites incorporated with hPLLA are related to the high crystallinity and crystalline morphologies of the PLLA matrix. Big spherulites lock a lot of MWCNTs at the intervals in the spherulites, which is harmful to the electrical conductivity. Small spherulites, with large surface areas, also need more MWCNTs to form conductive networks in the amorphous regions. Most MWCNTs that are bundled together to form conductive paths are found in samples with mid-sized spherulites of ∼6.7 µm. More interestingly, the high crystallinity and reconstructed MWCNT network also enhanced the Young modulus, elongation at break, and elastic modulus at high temperature of PLLA/MWCNT nanocomposites with small amounts of hPLLA.

Fully biobased and supertough polylactide-based thermoplastic vulcanizates fabricated by peroxide-induced dynamic vulcanization and interfacial compatibilization.

A fully biobased and supertough thermoplastic vulcanizate (TPV) consisting of polylactide (PLA) and a biobased vulcanized unsaturated aliphatic polyester elastomer (UPE) was fabricated via peroxide-induced dynamic vulcanization. Interfacial compatibilization between PLA and UPE took place during dynamic vulcanization, which was confirmed by gel measurement and NMR analysis. After vulcanization, the TPV exhibited a quasi cocontinuous morphology with vulcanized UPE compactly dispersed in PLA matrix, which was different from the pristine PLA/UPE blend, exhibiting typically phase-separated morphology with unvulcanized UPE droplets discretely dispersed in matrix. The TPV showed significantly improved tensile and impact toughness with values up to about 99.3 MJ/m(3) and 586.6 J/m, respectively, compared to those of 3.2 MJ/m(3) and 16.8 J/m for neat PLA, respectively. The toughening mechanisms under tensile and impact tests were investigated and deduced as massive shear yielding of the PLA matrix triggered by internal cavitation of VUPE. The fully biobased supertough PLA vulcanizate could serve as a promising alternative to traditional commodity plastics.

Fractional crystallization and homogeneous nucleation of confined PEG microdomains in PBS-PEG multiblock copolymers.

Fractional crystallization, homogeneous nucleation of poly(ethylene glycol) (PEG) segment, and self-nucleation behavior of PEG segment within miscible double crystalline poly(butylene succinate)-poly(ethylene glycol) (PBSEG) multiblock copolymers with different composition and segment chain length were studied by differential scanning calorimetry (DSC). Surface morphology of PBSEG10K with different PEG content was investigated by atomic force microscope (AFM). Different from di- or triblock copolymers, the microstructure and confinement of PEG dispersed phase in PBS matrix phase highly depends on chain length and sequence as well as segment content. The transition point of the PEG segment content from heterogeneous to homogeneous nucleation mechanism decreased from 50 to 39 wt % with PEG segment chain length increasing from 1000 to 2000 g/mol. When PEG segment chain length increased further to 6000 and 10000 g/mol, homogeneous nucleation phenomenon took place at much lower PEG content and fractional crystallization was observed at 29 and 24 wt %, respectively. Homogeneous nucleation mechanism of PBSEG(1K-36), PBSEG(2K-26), PBSEG(6K-19), and PBSEG(10K-12) was evidenced by the large supercoolings needed for crystallization, as well as first-order crystallization kinetics obtained. Self-nucleation behaviors of PEG segment still rely on the composition of PBSEGs. In the case of heterogeneous nucleation crystallization, self-nucleation behaviors of PEG segment showed standard self-nucleation behavior with classical three self-nucleation domains. When the crystallizable chains were confined into isolated microdomains, however, self-nucleation domain (domain II) disappeared. The absence of III(A) was observed in PBSEG(2K-39), while PBSEG(6K-29) had both III(A) and III(SA). Furthermore, AFM morphology studies still indicated the confined degree of PEG segment by previous PBS crystals was profoundly influenced by segment fraction. The confinement of the PEG segment by previous PBS edge-on lamellae was observed in the sample which displays a homogeneous nucleation crystallization behavior.

Urethane Ionic Groups Induced Rapid Crystallization of Biodegradable Poly(ethylene succinate).

Novel urethane ionic groups were incorporated into biodegradable poly(ethylene succinate) (PES) by chain extension reaction of PES diol (HO-PES-OH) and diethanolamine hydrochloride (DEAH) using hexamethylene diisocyanate (HDI) as a chain extender. The synthesized polymer was a novel segmented poly(ester urethane) ionomer (PESI) in which the soft segments were formed by reaction of HO-PES-OH with HDI and the hard segments that contained ionic groups were derived from reaction of DEAH with HDI. The crystallization rate of PESI was dramatically accelerated when 3 mol % urethane ionic groups were incorporated. However, the crystallization mechanism did not change. The significant acceleration in crystallization rate was attributed to the improved nucleation efficiency by incorporation of the urethane ionic group, because PESI showed significantly enhanced nucleation density but slightly slowed spherurlitic growth rate in comparison with PES which was synthesized by chain extension reaction of HO-PES-OH with HDI. The increased nucleation efficiency was ascribed to the aggregation of hard segments of PESI induced by the ionic interactions.

Chitin whiskers: an overview.

Chitin is the second most abundant semicrystalline polysaccharide. Like cellulose, the amorphous domains of chitin can also be removed under certain conditions such as acidolysis to give rise to crystallites in nanoscale, which are the so-called chitin nanocrystals or chitin whiskers (CHWs). CHW together with other organic nanoparticles such as cellulose whisker (CW) and starch nanocrystal show many advantages over traditional inorganic nanoparticles such as easy availability, nontoxicity, biodegradability, low density, and easy modification. They have been widely used as substitutes for inorganic nanoparticles in reinforcing polymer nanocomposites. The research and development of CHW related areas are much slower than those of CW. However, CHWs are still of strategic importance in the resource scarcity periods because of their abundant availability and special properties. During the past decade, increasing studies have been done on preparation of CHWs and their application in reinforcing polymer nanocomposites. Some other applications such as being used as feedstock to prepare chitosan nanoscaffolds have also been investigated. This Article is to review the recent development on CHW related studies.

Unique crystalline/crystalline polymer blends of poly(ethylene succinate) and poly(p-dioxanone): miscibility and crystallization behaviors.

Miscibility and crystallization behaviors of poly(ethylene succinate)/poly(p-dioxanone) (PES/PPDO) blends were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). PES/PPDO blends are completely miscible as proved by the single grass transition temperature (T(g)) dependence of composition and decreasing crystallization temperature of the blends in comparison with the respective component. POM observation suggests that simultaneous crystallization of PES and PPDO components in the blends took place, spherulites of one component can crystallize inside the spherulites of the other component, and the unique interpenetrated crystalline morphology has been formed for the blends in the full composition range. Isothermal crystallization kinetics of the blends was studied by DSC and the data were analyzed by the Avrami equation. The results suggest that the crystallization mechanisms of the blends were unchanged but the overall crystallization rates were slowed down compared with neat PES and neat PPDO. WAXD results indicate that the crystal structures of PES and PPDO did not change in the blends.

Structure and properties of soy protein/poly(butylene succinate) blends with improved compatibility.

A novel environmentally friendly thermoplastic soy protein/polyester blend was successfully prepared by blending soy protein isolate (SPI) with poly(butylene succinate) (PBS). To improve the compatibility between SPI and PBS, the polyester was pretreated by introducing different amounts of urethane and isocyanate groups before blending. The blends containing pretreated PBS showed much finer phase structures because of good dispersion of polyester in protein. Consequently, the tensile strength and modulus of blends increased obviously. A lower glass transition temperature of protein in the blends than that of the pure SPI, which was caused by the improvement of the compatibility between two phases, was observed by dynamic mechanical analyzer (DMA). The hydrophobicity, water resistance, and moisture absorption at different humidities of the blends were modified significantly due to the incorporation of PBS.