Improved Energy Harvesting Ability of Single-Layer Binary Fiber Nanocomposite Membrane for Multifunctional Wearable Hybrid Piezoelectric and Triboelectric Nanogenerator and Self-Powered Sensors.

While wearable self-powered electronic devices have shown promising improvements, substantial challenges persist in enhancing their electrical output and structural performance. In this work, a working mechanism involving simultaneous piezoelectric and triboelectric conversion within a monolayer-structured membrane is proposed. Single-layer binary fiber nanocomposite membranes (SBFNMs) (PVDF/CNTX@PAN/CNTX, DPCPCX) with two distinct interpenetrating nanocomposite fibers were created through co-electrospinning, incorporating multiwalled carbon nanotubes (CNTs) into polyvinylidene fluoride (PVDF) and polyacrylonitrile (PAN), respectively. The resulting membrane demonstrated an exceptional synergistic effect of piezoelectricity and triboelectricity along with a high machine-to-electric conversion capability. The addition of CNTs increased the PVDF ß-phase and the PAN planar zigzag conformation. As a result, the DPCPC0.5-SBFNMs-based piezoelectric nanogenerator exhibited excellent electrical output (187 V, 8.0 µA, and 1.52 W m-2), maintaining an exceptionally high level of output voltage compared with other piezoelectric nanogenerators. It successfully illuminated 50 commercial light-emitting diodes simultaneously. The output voltage of DPCPC0.5-SBFNMs was 5.1 and 4.6 times higher than that of PAN or PVDF single-fiber membranes, respectively. Furthermore, the peak voltage of DPCPC0.5-SBFNMs exceeded that of co-electrospinning PVDF/CNT1.0@PAN (DPCP1.0) and PVDF@PAN/CNT1.0 (DPPC1.0) by 20 and 10 V, respectively. The piezoelectric sensor made of DPCPC0.5-SBFNMs accurately sensed human movement, ranging from tiny to large, and demonstrated utility as an alarm in medical treatment, fire fighting, and monitoring. Endogenous triboelectricity is proposed in SBFNM piezoelectric materials, enhancing electromechanical conversion and electrical output capacity, thereby promising a wide application potential in self-powered wearable electronic devices.

3D printing of ultra-high viscosity resin by a linear scan-based vat photopolymerization system.

The current printing mechanism of the bottom-up vat photopolymerization 3D printing technique places a high demand on the fluidity of the UV-curable resin. Viscous high-performance acrylate oligomers are compounded with reactive diluents accordingly to prepare 3D printable UV-curable resins (up to 5000 cps of viscosity), yet original mechanical properties of the oligomers are sacrificed. In this work, an elaborated designed linear scan-based vat photopolymerization system is developed, allowing the adoption of printable UV-curable resins with high viscosity (> 600,000 cps). Briefly, this is realized by the employment of four rollers to create an isolated printing area on the resin tank, which enables the simultaneous curing of the resin and the detachment of cured part from the resin tank. To verify the applicability of this strategy, oligomer dominated UV-curable resin with great mechanical properties, but high viscosity is prepared and applied to the developed system. It is inspiring to find that high stress and strain elastomers and toughened materials could be facilely obtained. This developed vat photopolymerization system is expected to unblock the bottleneck of 3D printed material properties, and to build a better platform for researchers to prepare various materials with diversiform properties developed with 3D printing.

3D Printing of High Viscosity UV-Curable Resin for Highly Stretchable and Resilient Elastomer.

Elastomers prepared via vat photopolymerizationus ually exhibit unsatisfied mechanical properties owing to their insufficient growth of molecular weight upon UV exposure. Increasing the weight ratio of oligomer in the resin system is an effective approach to enhance the mechanical properties, yet the viscosity of the UV-curable resin increases dramatically; this hinders its printing. In this study, a linear scan-based vat photopolymerization (LSVP) system which can print high-viscosity resins is implemented to 3D print the oligomer-dominated UV-curable resin via a dual-curing mechanism. A polyurethane methacrylate blocking oligomer is first synthesized and then mixed with a commercialized bifunctional oligomer, photoinitiator, and primary amine as a chain extender to prepare high-viscosity UV-curable resin for the LSVP system. The deblocked isocyanate is further crosslinked with a chain extender via thermal treatment to construct a highly entangled polymer chain network. The optimal thermal treatment parameters are investigated, and the resilience of the 3D-printed elastomer is evaluated through continuous tensile loading and unloading tests. Subsequently, complex structured elastomers are printed, exhibiting favorable mechanical durability without defects. The results obtained from this work will provide a reference for preparing elastomeric devices with excellent physical properties and expand the application scope of vat photopolymerization to new fields.

Waterborne Polyurethane Acrylates Preparation towards 3D Printing for Sewage Treatment.

Conventional immobilized nitrifying bacteria technologies are limited to fixed beds with regular shapes such as spheres and cubes. To achieve a higher mass transfer capacity, a complex-structured cultivate bed with larger specific surface areas is usually expected. Direct ink writing (DIW) 3D printing technology is capable of preparing fixed beds where nitrifying bacteria are embedded in without geometry limitations. Nevertheless, conventional bacterial carrier materials for sewage treatment tend to easily collapse during printing procedures. Here, we developed a novel biocompatible waterborne polyurethane acrylate (WPUA) with favorable mechanical properties synthesized by introducing amino acids. End-capped by hydroxyethyl acrylate and mixed with sodium alginate (SA), a dual stimuli-responsive ink for DIW 3D printers was prepared. A robust and insoluble crosslinking network was formed by UV-curing and ion-exchange curing. This dual-cured network with a higher crosslinking density provides better recyclability and protection for cryogenic preservation. The corresponding results show that the nitrification efficiency for printed bioreactors reached 99.9% in 72 h, which is faster than unprinted samples and unmodified WPUA samples. This work provides an innovative immobilization method for 3D printing bacterial active structures and has high potential for future sewage treatment.

3D Printing Mechanically Robust and Transparent Polyurethane Elastomers for Stretchable Electronic Sensors.

Advanced stretchable electronic sensors with a complex structure place higher requirements on the mechanical properties and manufacturing process of the stretchable substrate materials. Herein, three kinds of polyurethane acrylate oligomers were synthesized successfully and mixed with a commercial acrylate monomer (isobornyl acrylate) to prepare photocurable resins with a low viscosity for a digital light processing three-dimensional (3D) printer without custom equipment. Results showed that the resin containing poly(tetrahydrofuran) units (PPTMGA-40) exhibited optimal mechanical properties and shape recoverability. The tensile strength and elongation at break of PPTMGA-40 were 15.7 MPa and 414.3%, respectively. The unprecedented fatigue resistance of PPTMGA-40 allowed it to withstand 100 compression cycles at 80% strain without fracture. The transmittance of PPTMGA-40 reached 89.4% at 550 nm, showing high transparency. An ionic hydrogel was coated on the surface of 3D-printed structures to fabricate stretchable sensors, and their conductivity, transparency, and mechanical performance were characterized. A robust piezoresistive strain sensor with a high strength (∼6 MPa) and a wearable finger guard sensor were fabricated, demonstrating that this hydrogel-elastomer system can meet the requirements of applications for advanced stretchable electronic sensors and expand the usage scope.

Structure-Property Relationship of Stereolithography Resins Containing Polysiloxane Core-Shell Nanoparticles.

Stereolithography (SL) is an additive manufacturing technique for fabricating bulk and delicate objects layer by layer using UV-curable resin. However, epoxy-based photocurable resins used in SL printers are commonly brittle due to the high cross-linking density, thus restricting the widespread adoption of SL. In an effort to overcome this drawback, this paper details an approach of toughening the resulting workpieces by incorporating polysiloxane core-shell nanoparticles (SCSP) into an epoxy-based, photocurable formulation. This approach attempted to attain both thermal stabilities and transparency qualities comparable to that of resin without SCSP. This work systematically analyzed how the shell thickness of the SCSP impacted the final properties of the printed product. Introducing 5% w/w SCSP with a diameter of approximately 132 nm into the resin improved strain at break measured by tensile and flexural tests by 745.5 and 248.6%, respectively, and increased the fracture toughness by 166.3%. Owing to the advantages of toughness, thermal stabilities, transparency, and high accuracy of epoxy-based photocurable resin with SCSP, the 3D printing nanocomposite developed here is capable of preparing a poly(methyl methacrylate) (PMMA)-like workpiece with a commercial SL 3D printer. These results may expand the scope of the application of 3D printing in a wide variety of industries.

High-Performance Cyanate Ester Resins with Interpenetration Networks for 3D Printing.

As the 3D printing technology is getting more and more popular and useful, demands for materials for 3D printing have increased significantly. Cyanate ester (CE) resin possesses the characteristics of high heat distortion temperature and high glass transition temperature, outstanding mechanical properties, low dielectric constant, and excellent water uptake. However, CE resin has not been widely used in 3D printing of UV curing because it is difficult for photopolymerizable groups to graft onto the chains of CE resin. On the other hand, the glass transition temperature (Tg) of the homopolymer of the tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA) outclasses that of other acrylates. Although THEICTA is particularly advantageous to prepare a UV-curing prepolymer with high glass transition temperature, it also cannot be directly used for fabricating heat-resistant 3D-printed parts because it is solid and adding diluents will reduce the thermal stability of printed objects. This study is unique in producing 3D-printed materials, in which the THEICTA tactfully dissolves in low viscosity (about 100 mPa·s under 25 °C) bisphenol E cyanate (BECy) without sacrificing two kinds of bulk material properties. In the process of 3D printing, the carbon-carbon double bonds from THEICTA are cured by radical polymerization. Postprinting thermal treatment transforms three cyanate groups to a triazine ring structure. Additionally, the two kinds of structures are interpenetrating. The high-performance 3D-printing material has potential in fields ranging from space flight and aviation to the automotive and electronic industry.

Dynamic Imine Bond-Based Shape Memory Polymers with Permanent Shape Reconfigurability for 4D Printing.

Shape memory polymer (SMP)-based 4D printing combines the advantages of SMP and 3D printing to form active materials with delicate structure. Nowadays, studies of SMP-based 4D printing materials mainly focus on cross-linked (meth)acrylate of which the permanent shape cannot be changed for their covalent linkage, limiting the usage of 4D printing materials. In this paper, a novel (meth)acrylate monomer with an aldehyde group (2-(methacryloyloxy)ethyl 4-formylbenzoate, MEFB) and hyperbranched cross-linker (HPASi) are synthesized to build (meth)acrylate systems (IEMSis) with dynamic imine bonds for 4D printing. The flexible chain structure of HPASi significantly enhances the toughness of IEMSis, which is 33-97-fold higher than that of the one without HPASi (IEM). The addition of HPASi also endows IEMSis good shape memory properties, and the shape fixity and shape recovery ratios of them are 97.5-97.6 and 91.4-93.7%, respectively. At the same time, IEMSis can undergo a stress relaxation process by dynamic exchanges of imine bonds under relatively mild conditions without a catalyst to acquire an ability of permanent shape reconfiguration. The shape retention ratio of IEMSi3 is 84.3%. In addition, the 4D-printed structures displayed here indicate that these 4D printing systems have a myriad of potential applications including aerospace structures, soft robotic grippers, smart electron switches, and intelligent packaging, while the reconfigurability shown by IEMSi3 will expand the scope of application fields of 4D printing materials.