Solvent Resistance Properties Research Articles

Enhancement of thermo-oxidative stability of polyimide composites by functionalized polyimide film surface modification

Polyimide (PI) resin-based composites exhibit excellent high-temperature resistance, solvent resistance, and mechanical properties, making them have broad application prospects in various fields such as aviation, aerospace, and transportation. With the continuous development of new devices, the requirements for the service temperature and service life of materials are improved, so there is an urgent need to improve the thermo-oxidative stability of polyimide composites. In this work, PI films, aluminum-coated PI film, and copper-coated PI film with low oxygen permeability were used as surface oxygen barrier materials, and surface film modified polyimide composites were prepared. The results show that, compared with the unmodified composite materials, after aging at 350°C for 400 hours, the weight loss rates of the composites modified by three kinds of surface films all increased by more than 50%, and the bending strength retention rates of the composites respectively increased by 47%, 51%, 45%, and the interlaminar shear strength retention rates respectively increased by 107%, 82%, 78%, showing excellent thermo-oxidative stability.

Thin film nanocomposite membrane ornamented with Z-scheme heterojunction carbon dot/NiFe–LDH for removal of organic contaminants from industrial wastewater

Removal of organics from wastewater is a tedious process and industries are looking for a facile, energy efficient strategy of wastewater treatment for producing clean water and recycling. Membrane technology is one of the efficient processes for wastewater treatment due to its energy efficient nature, simple operation and excellent performance. But, proneness of membrane fouling often limits its path to triumph. In this work, we have designed a ‘carbon dot/NiFe-layered double hydroxide (CD/NiFe–LDH)’ nanocomposite via in situ approach, which is coated on a poly(ethylene terephthalate) (PET) and cellulose based superhydrophillic membrane. The membrane is found to have excellent separation efficiency. The photocatalytic activity of CD/NiFe–LDH shows high oxidative degradation of the accumulated organics contaminants on the membrane surface providing self-cleaning ability and hence enhances the membrane’s lifetime. The membrane exhibits stable performance for 30 days continuous operation under UV-A light. The membrane flux is found to be ∼42 Lm−2 h−1 and 48 Lm−2 h−1 for crude oil–water emulsion and phenol respectively while rejection around ≥99 % is obtained for the both. The flux recovery ratio (FRR) of the post photo irradiated membrane is found to be 88.07 %. The membrane also shows organic solvent resistance property and prevents bacterial pathogens in wastewater.

Physical Crosslinking of Aqueous Polymer Dispersions: A Perspective

AbstractColloidal polymers, and in particular aqueous polymer dispersions, are widely used in commercial applications such as coatings and adhesives. Historically, the solvent resistance and mechanical properties of these systems have been improved by covalently crosslinking the polymer chains after drying. More recently, work has been directed toward replacing this covalent crosslinking, which typically involves highly reactive functional groups, by physical crosslinking through the use of supramolecular interactions. While conceptually similar to the use of covalent crosslinking, physical crosslinking has a unique influence on the rheology of the polymer, which leads to substantial differences in the development of mechanical strength during drying, as well as the mechanical properties of the final polymer film. In this perspective, the advantages and challenges of this approach are outlined, and an outlook for future research in this direction is provided.

Bio-based ester- and ester-imine resins for digital light processing 3D printing: The role of the chemical structure on reprocessability and susceptibility to biodegradation under simulated industrial composting conditions

Four biobased ester and ester-imine photocurable resins were formulated and evaluated for printability by digital light processing 3D printing. The resin formulations consisted of methacrylated eugenol alone or in combination with methacrylated poly(hydroxybutyrate)-oligomers and/or methacrylated vanillin-derived Schiff-base monomers. It was not possible to print methacrylated eugenol alone into coherent thermosets, likely due to the lower reactivity of the allyl-double bond. However, in combination with the other building blocks methacrylated eugenol improved the printability, although some over-curing phenomena were registered especially for the resins composed of methacrylated eugenol and methacrylated poly(hydroxybutyrate)-derived oligomers. The three formulations that were successfully printed to coherent thermosets were further evaluated for their solvent resistance, thermal and mechanical properties, reprocessability and biodegradability under simulated industrial composting conditions. The reprocessing experiments documented the synergic effect of ester and imine dynamic covalent bonds in favoring the preservation of the elastic modulus of the thermosets; while an evidently higher deterioration of the mechanical properties was registered for the ester-thermosets. The biodegradation studies highlighted a clear correlation between the biodegradation rate and the chemical structure of the thermosets, with the aliphatic components and ester and imine bonds increasing the thermosets’ susceptibility to the biodegradation under simulated industrial composting conditions.

The robust design of PMIA braided tube reinforced PFA hollow fiber membranes with graphene doping for water-in-oil separation

In order to solve the problem of oily wastewater, the poly(m-phenyleneisophthalamide)(PMIA) braided tube reinforced (PBR) poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether)(PFA) hollow fiber membrane with thermal and solvent resistant property was prepared via no-solvent green method. The membrane surface and pore structure was optimized by changing the sintering temperature and graphene (GE) content. The morphologies showed that the spherical surface with good lipophilicity was formed, and the excellent mechanical strength with favorable interface bonding state could be obtained due to the PFA melts permeating into the supporting layer. The doping of GE produced synergistic effects with the sintering temperature owing to its good thermal conductivity and pore formation. The PBR-PFA/GE hollow fiber membrane exhibited good hydrophobicity and lipophilicity with more than 97% separation efficiency for different oil products at -0.02 MPa. With the addition of GE, the average pore size first increases and then decreases, and the porosity gradually decreases. In addition, the hollow fiber membrane showed high separation ability to the water-in-oil emulsion, and maintained stable flux recovery rate after recycling, making it possible to apply in the field of oily wastewater treatment.

Preparation of Graphene Oxide/Polymer Hybrid Microcapsules via Photopolymerization for Double Self-Healing Anticorrosion Coatings.

In this work, graphene oxide (GO)/polymer hybrid microcapsule-loaded self-healing agents were prepared via the combination of the emulsion template method and photopolymerization technology. The incorporation of GO in the microcapsule shell not only improved the impermeability, mechanical property, and solvent resistance property of the microcapsules significantly but also endowed the microcapsules with photothermal conversion property. By incorporating GO/polymer hybrid microcapsules in water-borne epoxy resin, a novel kind of anticorrosion coating with a double self-healing property was successfully fabricated. When the coating was scratched, the linseed oil (LO) encapsulated in the microcapsules could fill the crack, and the photothermal conversion property of GO could promote the molecular chain movement of the damaged area under near-infrared (NIR) irradiation to realize the close of the crack. Based on the filling of LO and photothermal conversion-induced scratch narrowing, the "filling" and "close" double self-healing effect can be realized under temporal NIR irradiation, which could lead to the complete recovery of the scratched coating. The |Z|f=0.1Hz value of the damaged coating with GO/polymer microcapsules after double healing was comparable to that of the intact coating, which was about 4 orders of magnitude higher than that of the scratched blank coating and single self-healing coating. As to the neutral salt spray test, the scratched blank coating failed in protection after 100 h, while the healed composite coating did not show any corrosion after 300 h.

One-step facile pathway synthesis of PAPXD/1214-PEA thermoplastic elastomer: Structure and properties

In this study, a novel and facile one-step synthesis route was conducted to prepare semi-aromatic polyamide elastomer (PAPXD/1214-PEA) with p-phenylenediamine, dodecane diamine, dodecanedioic acid and polyether amine (PEA) as monomers. A systematic investigation has been conducted into the effect of hard segment content on the thermal, mechanical and solvent resistance of polymers when semi-aromatic polyamides are used as hard segments. It was found that the melting point of the copolymers gradually increased from 191.2 °C to 231.5 °C with the hard segment content increased from 39 % to 76 %, while the Vicat softening temperature (VST) enhanced from 103.2 °C to 192.2 °C. Compared with the commercial polyamide elastomer Pebax@ (produced by Arkema Inc) with similar hard segment contents, the VST of PAPXD14/1214-PEA were 17.4–66.2 °C higher. The mechanical performance of these elastomers was also largely improved with tensile strength increasing from 15.1 to 40.6 MPa, Young's modulus from 28.2 to 168.7 MPa, toughness from 91.1 to 170.7 MJ/m3. In addition, the solvent resistance properties of PAPXD14/1214-PEA was compared with the commercial polyamide elastomer Pebax@. After soaking in hydrochloric acid for 24 h, the tensile strength of PAPXD/1214-PEA with the hard segment content increased from 50 % to 63 % decreased down to 9.4 and 14.4 MPa, respectively. While the commercial polyamide elastomer Pebax@ (with similar hard segment content) decreased down to 1.5 and 4.3 MPa, indicating the commercial polyamide elastomer products were deteriorated. This suggests the corrosion resistance of the synthesized PAPXD/1214-PEA is much better than that of commercial product, and these semi-aromatic polyamide elastomers can be potentially applied in some harsh service environment especially for high temperature and corrosion sealing.

Development of cellulose/ZnO based bioplastics with enhanced gas barrier, UV-shielding effect and antibacterial activity

Development of renewable and biodegradable plastics with good properties, such as the gas barrier, UV-shielding, solvent resistance, and antibacterial activity, remains a challenge. Herein, cellulose/ZnO based bioplastics were fabricated by dissolving cellulose carbamate in an aqueous solution of NaOH/Zn(OH)42−, followed by coagulation in aqueous Na2SO4 solution, and subsequent hot-pressing. The carbamate groups detached from cellulose, and ZnO which transformed from cosolvent to nanofiller was uniformly immobilized in the cellulose matrix during the dissolution/regeneration process. The appropriate addition of ZnO (below 10.67 wt%) not only improved the mechanical properties but also enhanced the water and oxygen barrier properties of the material. Additionally, our cellulose/ZnO based bioplastic demonstrated excellent UV-blocking capabilities, increased water contact angle, and enhanced antibacterial activity against S. aureus and E. coli, deriving from the incorporation of ZnO nanoparticles. Furthermore, the material exhibited resistance to organic solvents such as acetone, THF, and toluene. Indeed, the herein developed cellulose/ZnO based bioplastic presents a promising candidate to replace petrochemical plastics in various applications, such as plastic toys, anti-UV guardrails, window shades, and oil storage containers, offering a combination of favorable mechanical, gas barrier, UV-blocking, antibacterial, and solvent-resistant properties.

Enhancing interfacial solvent resistance and mechanical properties of carbon fiber/polyether ether ketone composites with water‐borne sizing agents based on cross‐linkable polyphthalonitrile

AbstractThe inherent structural properties and elevated processing temperatures of thermoplastic resins present new challenges in the realm of carbon fiber (CF) sizing agents. Consequently, a water‐based cross‐linkable nitro‐phthalonitrile capped polyfluorenyl ether ketone sizing agent was meticulously designed. The sizing agent exhibits superior storage stability, encapsulating particles spanning dimensions from 66.51 to 87.71 nm. The inherent mechanism during the hot‐pressing stage involves a self‐crosslinking of nitrile groups toward stable structures with unparalleled resistance to solvents. The crosslinked sizing agent boasts a remarkable glass‐transition temperature of 290°C. Noteworthy, significance is the consequential 40.1% augmentation in maximum flexural strength, along with a commendable 35% increase in interlaminar shear strength for CF‐1.5/PEEK composites in contrast to their unsized CF/PEEK counterparts. In summary, the focal aspiration of this research endeavor lies in offering a straightforward and viable methodology for the exploration of cross‐linkable sizing agents, strategically catering to both “thermoplastic processing” and “thermosetting applications.”Highlights Bulky fluorenyl unit increases the intermolecular volume of copolymer poly(fluorenyl ether ketone). The introduction of the BPF unit to the molecular elevates the thermal stability of the copolymer. Unique electron‐donating proclivity of the fluorenyl group drastically improved its reactivity. The polymerization was accomplished at a relatively low temperature of 150°C for practical applications. The ILSS, IFSS, and bending strength were noteworthy increased by 35%, 74.02%, and 40.1%

Preparation and properties of high molecular weight high temperature resistant carborane polyurethane adhesive

The long-term use temperature of the traditional high-temperature adhesive can only reach about 280 °C, and it cannot be used in extreme environments such as acid and alkali for a long time, which greatly limits its application in aerospace and other fields. Because of its unique three-dimensional structure, carborane has excellent thermal stability and chemical stability. Based on this, first, this article introduced carborane monomer into polyurethane structure, using indirect copolymerization method, Hydroxyl carborane derivative (m8) and conventional polyether diols were used as soft segments. By adjusting the introduction ratio of m8, a series of copolymerized carborane polyurethane (Co-CBR-PU) with controllable thermal and mechanical properties were successfully prepared. Its structure and molecular weight were characterized by FTIR and gel permeation chromatography (GPC), its surface morphology were observed by SEM. The thermal stability and mechanical properties were studied by thermogravimetric test, tensile test and rheological dynamic mechanical analysis test., and its activity, solvent resistance and hydrophobic properties were studied by finger contact method, solvent resistance test and contact Angle test. Second, the high temperature resistant carborane polyurethane adhesive (PUAS) was prepared using Co-CBR-PU as matrix and its adhesion was studied. The results show that a series of Co-CBR-PU has good high temperature resistance, mechanical properties and solvent resistance after adding carborane monomer, and its various properties were optimal when the addition amount of m8 was 15 wt%. The carborane PUAS prepared by using it as the substrate has excellent high temperature adhesion to different adhesive parts. The aim of this study is to reduce the cost of synthesis of carborane polyurethane by regulating the proportion of carborane, and then realize the industrial trial production of high temperature resistant carborane adhesive.

Few-cycle atomic layer deposition to nanoengineer polybenzimidazole for H2/CO2 separation

Atomic layer deposition (ALD) creates uniform sub-nanometer films on a variety of surfaces and nanopore walls and has been used to modify polymers to improve surface affinity towards specific molecules, solvent resistance, and barrier properties to gases and vapors. Here, for the first time, we demonstrate that few-cycle ALD can be used to engineer functional polymers at a sub-nanometer scale to improve both molecular size-sieving ability and counterintuitively, gas permeability. Particularly, 1-cycle ALD treatment of polybenzimidazole (PBI) by sequential exposure to trimethylaluminum (TMA) and water vapor remarkably increases H2 permeability by 120% − 270% and H2/CO2 selectivity by 30% at 35–200 °C. The ALD not only deposits an AlOx layer on the surface but also enables the TMA to infiltrate and react with the bulk PBI to form an AlOx network, disrupting polymer chain packing and increasing chain rigidity. The membrane exhibits excellent stability when challenged with simulated syngas, overcoming the permeability/selectivity tradeoff for H2/CO2 separation. This study showcases a facile and scalable way of engineering polymeric membranes at a sub-nanometer level to improve molecular separation performance.

Rapid Reassembly, Biomass-Derived Adhesive Based on Soybean Oil and Diels-Alder Bonds.

Synthetic adhesives play a crucial role in holding together solid materials through interfacial interactions. Thermoplastic and thermosetting adhesives are important types of synthetic adhesives, with thermoplastic adhesives being reassemblable and thermosetting adhesives exhibiting high adhesive strength and creep resistance. However, there is a need to combine the advantages of both types and develop high bonding strength, reassemblable adhesives. Here, epoxidized soybean oil (ESO) was used to prepare adhesive networks and Diels-Alder bonds were incorporated to enhance reassembly ability. The ESO was functionalized with furyl groups and cross-linked via the reaction between furyl and imide groups to involve the Diels-Alder bonds. The resulting adhesive exhibited good solvent resistance and mechanical properties, which could be regulated by adjusting the quantity of cross-linker. The prepared adhesives also demonstrated self-healing capabilities, as the scratch on the surface gradually diminished with heating. Additionally, the adhesives showed the ability to undergo recycling without significant changes in properties. The prepared adhesives exhibited hydrophilicity and the flow characteristics during reassembly were characterized by a decrease in torque. This study provides a promising approach for the development of synthetic adhesives with reassembly ability, which has important implications for the field of bonding.

Lowering spinning temperature for polyketone (PK) hollow fiber membrane fabrication with low-toxic diluent system via thermally induced phase separation

Due to the excellent solvent resistance properties of polyketone (PK), the traditional non-solvent induced phase separation (NIPS) preparation process is both highly toxic and complex. In this work, we successfully and efficiently prepared PK hollow fiber membranes using the thermally induced phase separation (TIPS) method, capitalizing on a low-toxicity diluent system of polyethylene glycol 300 (PEG300) and triethylene glycol (TEG). Moreover, by simply adding TEG to the diluent, we achieved a reduction in the spinning temperature, resulting in membranes that display an interconnected structure formed through the liquid-liquid phase separation process. We systematically investigated the impact of the TEG ratio in the diluent, PK concentration, and propylene carbonate (PC) ratio in the bore liquid on the phase diagram, membrane morphology, and characteristics of PK membranes. Increasing the PC ratio in the bore liquid significantly improves the inner surface porosity due to PC penetration into the dope solution, leading to high water permeability. Additionally, the resulting PK membrane exhibits exceptional resistance to organic solvents. This work introduces a novel approach to lower the spinning temperature for PK membrane preparation in the TIPS process while preserving the membrane structure and properties.

Simple Non-Equilibrium Atmospheric Plasma Post-Treatment Strategy for Surface Coating of Digital Light Processed 3D-Printed Vanillin-Based Schiff-Base Thermosets.

A simple non-equilibrium atmospheric plasma post-treatment strategy was developed for the surface coating of three-dimensional (3D) structures produced by digital light processing 3D printing. The influence of non-equilibrium atmospheric plasma on the chemical and physical properties of vanillin-derived Schiff-base thermosets and the dip-coating process was investigated and compared to the influence of traditional post-treatment with UV-light. As a comparison, thermosets without post-treatment were also subjected to the coating procedure. The results document that UV post-treatment can induce the completion of the curing of the printed thermosets if complete curing is not reached during printing. Conversely, the plasma post-treatment does not contribute to the curing of the thermoset but causes some opening of the imine bonds and the regeneration of aldehyde functions. As a consequence, no great differences are observed between the not post-treated and plasma post-treated samples in terms of mechanical, thermal, and solvent-resistant properties. In contrast to the UV post-treatment, the plasma post-treatment of the thermosets induces a noticeable increase of the thermoset hydrophilicity ascribed to the reformation of amines on the thermoset surface. The successful coating process and the greatest uniformity of the lignosulfonate coating on the surface of plasma post-treated samples are considered to be due to the presence of these amines and aldehydes. The investigation of the UV shielding properties and antioxidant activities documents the increase of both properties with the increasing amount and uniformity of the formed coating. Interestingly, evident antioxidant properties are also shown by the noncoated thermosets, which are deduced to their chemical structures.

Digital Light Processing 3D Printing of Isosorbide- and Vanillin-Based Ester and Ester-Imine Thermosets: Structure-Property Recyclability Relationships.

Four isosorbide-based photocurable resins were designed to reveal correlations between the composition and chemical structure, digital light processing (DLP) three-dimensional (3D) printability, thermoset properties, and recyclability. Especially, the role of functional groups, i.e., the concentration of ester groups vs the combination of ester and imine functionalities, in the recyclability of the resins was investigated. The resins consisted of methacrylated isosorbide alone or in combination with methacrylated vanillin or a flexible methacrylated vanillin Schiff-base. The composition of the resins significantly affected their 3D printability as well as the physical and chemical properties of the resulting thermosets. The results indicated the potential of methacrylated isosorbide to confer rigidity to thermosets with some negative effects on the printing quality and solvent-resistance properties. An increase in the methacrylated vanillin concentration in the resin enabled us to overcome these drawbacks, leading, however, to thermosets with lower thermal stability. The replacement of methacrylated vanillin with the methacrylated Schiff-base resin decreased the rigidity of the networks, ensuring, on the other hand, improved solvent-resistance properties. The results highlighted an almost complete preservation of the elastic modulus after the reprocessing or chemical recycling of the ester-imine thermosets, thanks to the presence of two distinct dynamic covalent bonds in the network; however, the concentration of the ester functions in the ester thermosets played a significant role in the success of the chemical recycling procedure.

Synthesis of dendritic urethane acrylates for fabricating a robust honeycomb-like structure acting for SERS detection

In this study, novel dendritic urethane acrylate polymers were developed for the fabrication of robust honeycomb-like surfaces after exposure to a UV-crosslinking process. Through iterative synthesis based on a highly selective intermediate of 4-isocyanate-4′-(3,3-dimethyl-2,4-dioxo-azetidine)-diphenylmethane, poly(urea/malonamide) dendrons bearing peripheral methyl methacrylate end groups with well-defined structures were realized. A coating solution was prepared by the combined use of 30–70 wt% UA dendron acting as dendritic diluents and dendritic UA copolymers acting as amphiphiles that can fabricate honeycomb-like surfaces via a breath figure self-assembly process using water droplets as templates. The resulting film can be cured under UV light to achieve a robust honeycomb-like structure with a hexagonal structure exhibiting solvent-resistant properties in ethanol. Consequently, this solvent-resistant porous array can act as a substrate for the detection of vanishingly low concentrations of analytes that are aqueous insoluble via surface-enhanced Raman scattering analysis.

Robust SiO2/polymer hybrid microcapsule synthesized via emulsion photo-polymerization and its application in self-lubricating coatings

In this work, a novel kind of SiO2/polymer hybrid microcapsule encapsulating lubricant oil was prepared via a facile one-pot emulsion photo-polymerization method. In our strategy, an emulsion with the oil phase composed of SiO2 particles, photo-curable prepolymer, dichloromethane, photo-initiator and lubricant oil was firstly prepared. In the process of solvent evaporation, phase separation occurred between the photo-curable prepolymer and lubricant oil, and SiO2 particles migrated to the oil-water interface. After UV irradiation, the photo-curable prepolymer was photo-polymerized to form microcapsule shell, and SiO2/polymer hybrid microcapsule was yielded. The whole process could be finished within several minutes at room temperature, which was energy-saving and time-saving. The surface morphology of the microcapsule and the element distribution on the surface of the shell were investigated by SEM and EDS. The solvent resistance and mechanical property of hybrid microcapsules were tested. The morphology, the solvent resistance and the mechanical properties of SiO2/polymer hybrid microcapsule was controlled by adjusting the amount of SiO2 particles added in the oil phase. It was found that the introduction of SiO2 in the microcapsule shell could significantly improve the solvent resistance and mechanical properties of microcapsule. The synthesized hybrid microcapsule was embedded into epoxy resin for fabricating self-lubricating coatings. The friction and wear test results showed that the tribological property of the epoxy resin coating was significantly improved with the incorporation of the microcapsule. When the content of SiO2/polymer microcapsules was 10 wt%, the friction coefficient of the composite coating was 0.062, almost one-tenth of that of the pure epoxy coating (0.53).

Polybenzimidazole: a novel, fluorocarbon-free, SPME sorbent binder with good thermal and solvent resistance properties for GC and LC analysis.

A novel solid-phase microextraction (SPME) coating is presentedthat uses polybenzimidazole (PBI) as a binder to immobilize micro-size sorbent particles onto a support. An evaluation of the developed binder's thermal and solvent desorption capabilities demonstrated its compatibility with both gas and liquid chromatography (GC and LC). The incorporation of hydrophilic-lipophilic balanced (HLB) particles provided optimal extraction coverage for an array of chemically diverse analytes possessing a range of hydrophobicities and molecular weights. The developed binder's performance was assessed by comparing it to a selection of binders commonly used in the literature, including polydimethylsiloxane (PDMS) and polyacrylonitrile (PAN), as well as the more recently developed polyvinylidene fluoride (PVDF) and polytetrafluoroethylene amorphous fluoroplastic (PTFE AF 2400). The results revealed that PBI provides better performance compared to PVDF and PTFE AF 2400 in terms of its environmental impact, while also being convenient for use in coating preparation and offering good matrix compatibility. The thermal analysis revealed that PBI exhibited more than 93% weight retention at 550°C, which is superior to PVDF's 80.07% weight retention at 393.78°C. To the best of our knowledge, this work is the first to use PBI as a particle binder in SPME coatings. The PBI coating maintained high extraction efficiencies under extreme conditions with pH values of 3 and 12. The performance of PBI in combination with HLB was assessed by employing it to extract several drugs of abuse and McReynolds compounds for LC and GC analysis, respectively. The results indicated that PBI performs similarly to PAN for LC but is outperformed by PDMS in GC applications with respect to extraction and desorption kinetics. Nonetheless, the thermal and solvent desorption results indicated that PBI can be used for both applications, as it remains stable at temperatures over 350°C and isstable when solvent desorption is applied.

Cationically photocured epoxy/polycaprolactone materials processed by solution electrospinning, melt electrowriting and 3D printing: Morphology and shape memory properties

Epoxy/polycaprolactone (PCL) blends containing cationic photo-initiator were prepared by both solution and melt blending. These materials were processed by solvent casting, solution electrospinning (SE), melt electrowriting (MEW), and Fused Deposition Modeling (FDM) 3D printing. The final materials were obtained after UV curing at room temperature. FTIR, and gel content measurements showed that all the materials were crosslinked and that the PCL was part of the network. The shape memory abilities (measured by DMA experiments) depended on the processing technique. Thus, the fixity and recovery ratios were optimal for electrospun fibers, while the 3D printed sample was not able to recover any shape, probably because of the poor adhesion between the printed layers. According to AFM images, samples obtained by MEW and 3D printing produced materials with spherulitic morphology, while solution electrospinning rendered fibers with Shish-Kebab-type crystalline morphology. The latter was highly anisotropic, and many chains were oriented along the nanofiber axis interdispersed with amorphous regions where the epoxy resin formed covalent links with the PCL chains. This morphology conferred extraordinary solvent resistance and shape memory properties to the electrospun mats. The latter manifested a very high affinity towards chloroform, and accordingly, they displayed potential applications as chloroform sensors.

Versatile Fabrication of Polymer Microcapsules with Controlled Shell Composition and Tunable Performance via Photopolymerization

In this work, a series of polymer microcapsules based on UV-curable prepolymers are prepared by combining an emulsion template and photopolymerization. The modulation of the shell structure is achieved by employing UV-curable prepolymers with different chemical structures (polyurethane acrylates, polyester acrylates, and epoxy acrylates) and functionalities (di-, tetra-, and hex-). The relationships between the shell structure and the microcapsule properties are investigated in detail. The results show that the properties of the microcapsules can be effectively regulated by adjusting the composition and cross-linking density of the shell. Epoxy acrylate-based microcapsules exhibit higher impermeability, solvent resistance, and barrier and mechanical properties than polyurethane acrylate and polyester acrylate-based microcapsules. Using UV-curable prepolymer with high functionality as a shell-forming material could effectively improve the impermeability, solvent resistance, and barrier and mechanical properties of microcapsules. In addition, the dispersion of microcapsules in the coating matrix tends to follow the "similar component, better compatibility" principle, i.e., a uniform dispersion of the microcapsule in the coating matrix is more easily achieved when the compositions of the microcapsule shell and coating are similar in structure. The convenient adjustment of the shell structure and the investigation of the "structure-property" relationship provide guidance for the further controlled design of microcapsules.