3D Printed Conformal Strain and Humidity Sensors for Human Motion Prediction and Health Monitoring via Machine Learning.

Wearable sensors have garnered considerable attention due to their flexibility and lightweight characteristics in the realm of healthcare applications. However, developing robust wearable sensors with facile fabrication and good conformity remains a challenge. In this study, a conductive graphene nanoplate-carbon nanotube (GC) ink is synthesized for multi jet fusion (MJF) printing. The layer-by-layer fabrication process of MJF not only improves the mechanical and flame-retardant properties of the printed GC sensor but also bolsters its robustness and sensitivity. The direction of sensor bending significantly impacts the relative resistance changes, allowing for precise investigations of joint motions in the human body, such as those of the fingers, wrists, elbows, necks, and knees. Furthermore, the data of resistance changes collected by the GC sensor are utilized to train a support vector machine with a 95.83% accuracy rate for predicting human motions. Due to its stable humidity sensitivity, the sensor also demonstrates excellent performance in monitoring human breath and predicting breath modes (normal, fast, and deep breath), thereby expanding its potential applications in healthcare. This work opens up new avenues for using MJF-printed wearable sensors for a variety of healthcare applications.

4D Printing of Reprogrammable Liquid Crystal Elastomers with Synergistic Photochromism and Photoactuation.

4D printing of liquid crystal elastomers (LCEs) via direct ink writing has opened up great opportunities to create stimuli-responsive actuations for applications such as soft robotics. However, most 4D-printed LCEs are limited to thermal actuation and fixed shape morphing, posing a challenge for achieving multiple programmable functionalities and reprogrammability. Here, a 4D-printable photochromic titanium-based nanocrystal (TiNC)/LCE composite ink is developed, which enables the reprogrammable photochromism and photoactuation of a single 4D-printed architecture. The printed TiNC/LCE composite exhibits reversible color-switching between white and black in response to ultraviolet (UV) irradiation and oxygen exposure. Upon near-infrared (NIR) irradiation, the UV-irradiated region can undergo photothermal actuation, allowing for robust grasping and weightlifting. By precisely controlling the structural design and the light irradiation, the single 4D-printed TiNC/LCE object can be globally or locally programmed, erased, and reprogrammed to achieve desirable photocontrollable color patterns and 3D structure constructions, such as barcode patterns and origami- and kirigami-inspired structures. This work provides a novel concept for designing and engineering adaptive structures with unique and tunable multifunctionalities, which have potential applications in biomimetic soft robotics, smart construction engineering, camouflage, multilevel information storage, etc.

Spectroscopic Identification of Active Sites of Oxygen-Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide.

The electrochemical synthesis of hydrogen peroxide (H2 O2 ) via a two-electron (2 e- ) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst for H2 O2 electrochemical production. The optimized PCC900 material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2 O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.

Surface Modification of Hetero-phase Nanoparticles for Low-Cost Solution-Processable High-k Dielectric Polymer Nanocomposites.

The surface modification of nanoparticles (NPs) is crucial for fabricating polymer nanocomposites (NCs) with high dielectric permittivity. Here, we systematically studied the effect of surface functionalization of TiO2 and BaTiO3 NPs to enhance the dielectric permittivity of polyvinylidene fluoride (PVDF) NCs by 23 and 74%, respectively, measured at a frequency of 1 kHz. To further increase the dielectric permittivity of PVDF/NPs-based NCs, we developed a new hetero-phase filler-based approach that is cost-effective and easy to implement. At a 1:3 mixing ratio of TiO2:BaTiO3 NPs, the dielectric constant of the ensuing NC is found to be 50.2, which is comparable with the functionalized BaTiO3-based NC. The highest dielectric constant value of 76.1 measured at 1 kHz was achieved using the (3-aminopropyl)triethoxysilane (APTES)-modified hetero-phase-based PVDF composite at a volume concentration of 5%. This work is an important step toward inexpensive and easy-to-process high-k nanocomposite dielectrics.

Hindered phenolic antioxidant passivation of black phosphorus affords air stability and free radical quenching.

As an antioxidant, hindered phenol scavenges free radicals. Due to the oxidative degradation of black phosphorus (BP) in the presence of water and oxygen, free radical quenching of hindered phenol antioxidants can solve this issue and improve the environmental stability and flame retardant efficiency of BP. Herein, hydroxyl-modified BP (BP-OH) with active groups on the surface was obtained by hydroxylation, and then the hindered phenol antioxidant was grafted onto the surface of BP-OH through an isophorone diisocyanate bridging covalent reaction to obtain hindered phenol-modified BP (BP-HPL). The fire hazard of thermoplastic polyurethane (TPU) can be significantly reduced by introducing BP-HPL into TPU. Adding 2 wt% BP-HPL can reduce the heat release rate and total heat release values of TPU by 49.9% and 49.0%, respectively. In addition, the reductions in smoke volume and carbon monoxide production were also significant. Compared with BP-OH, the environmental stability of BP-HPL is significantly improved. This work provides a reference for the application of BP in the field of fire safety and simultaneously achieves the improvement of the environmental stability and flame retardant performance of BP.

Hierarchical Structure: An effective Strategy to Enhance the Mechanical Performance and Fire Safety of Unsaturated Polyester Resin.

It is still a big challenge to prepare polymer/layered double hydroxide (LDH) composites with high performance, due to the strong agglomeration tendency of LDHs in the polymeric matrix. In this study, to avoid the agglomerated situation, the orientated LDH nanosheets were vertically grown on a ramie fabric surface, which was then embedded in unsaturated polyester resin (UPR) through the combination method of hand lay-up and vacuum bag. Due to the increased contact area and the restricted interfacial slip in the in-plane direction, the hierarchically LDH-functionalized ramie fabrics (denoted as Textile@LDH) significantly enhanced the mechanical performance of UPR composites. Then, the phosphorus- and silicon-containing coating (PSi) was used for the further improvement of the interfacial adhesion. The tensile strength of UPR/Textile@LDH@PSi composites increased by 121.67%, compared to that of neat UPR. The reinforcement mechanism was studied through analyzing the surface nano/microstructure and wetting properties of the raw and modified textiles, as well as the interfacial interaction between the ramie fabrics and UPR. Meanwhile, the thermal stability, thermal conductivity, and flame-retardant performance of ramie-reinforced UPR composites were improved. Particularly, as-prepared hierarchical Textile@LDH@PSi inhibited the heat release during the combustion process of fabric-reinforced UPR composites, and the peak heat release rate and total heat release values decreased by 36.56 and 47.57%, respectively, compared with the neat UPR/Textile composites. The suppression mechanism was further explored by analyzing the microstructure and chemical compositions of char residues. This research paved a feasible solution to improve the poor dispersion of LDHs in polymers and prepared the high-performance UPR composites with multifunctional applications.

Bi2Se3 decorated recyclable liquid-exfoliated MoS2 nanosheets: Towards suppress smoke emission and improve mechanical properties of epoxy resin.

Bimetallic compounds have been proved superior suppression effect on smoke emission during combustion of polymers. In this work, MoS2/Bi2Se3 (MB) hybrids were prepared by a facile wet chemical method and showed superior performance on smoke suppression of EP matrix during combustion. N-vinyl pyrrolidone (NVP) was employed to exfoliate molybdenum disulfide (MoS2) nanosheets in a recyclable method, which showed high efficiency and was recyclable. Exfoliated MoS2 exhibited large surface area and used as carriers to synthesize MB hybrids. Considering the catalytic effect of bismuth and molybdenum, the hybrids had a great influence on the smoke emission behaviors of EP composites. The smoke production was obviously suppressed during the flaming combustion (more than 22% and 23% decrease obtained from cone calorimeter and steady state tube furnace, respectively) or smolder processes (more than 23% decrease obtained from smoke chamber) at only 1 wt% content of MB hybrids. What's more, due to superior dispersion state, the addition of MB hybrids also enhanced the mechanical properties of EP matrix, including wear resistance and tensile property. This work provided a safe and green exfoliation method of MoS2 to prepare polymers/MoS2 composites and also constructed a novel binary hybrids for enhancing combination performances of polymers.

Construction of Hierarchical Natural Fabric Surface Structure Based on Two-Dimensional Boron Nitride Nanosheets and Its Application for Preparing Biobased Toughened Unsaturated Polyester Resin Composites.

It has been a big challenge to prepare the unsaturated polyester resin (UPR) composites with good fire safety, interfacial quality, and impact strength in an environmentally friendly way. In this study, to improve interfacial performance of fabric-reinforced UPR composites, nontoxic two-dimensional hexagonal boron nitride (h-BN) nanosheets were assembled on the surface of ramie fabrics, where sodium alginate acts as a green dispersant to disperse h-BN sheets during the process. Then, the biobased phosphorus-containing toughening agent (PCTA) was synthesized to simultaneously improve the impact strength and fire safety of the composite. With application of h-BN nanosheets-assembled fabric (AF) and 20 wt % of PCTA, the AF/UPR@PCTA20 composite presented the maximum 41.2% decrease in the value of peak heat release rate and a maximum 17.8% decrease in the value of total heat release, which also reached V-0 rating in the vertical burning test. Meanwhile, the AF/UPR@PCTA20 composite showed an obvious increase in limiting oxygen index, from 24.0 to 29.5% compared with RF/UPR. The flame retardant mechanism was investigated from gas phase and condensed phase. Furthermore, compared to neat RF/UPR composite, the AF/UPR@PCTA20 composite showed a significant 68.8% improvement in impact strength, implying an extreme toughening effect of PCTA on UPR composites. The research provides a viable green method for the development of environmentally friendly UPR composites in the future.

Rapid Synthesis of Oxygen-Rich Covalent C2N (CNO) Nanosheets by Sacrifice of HKUST-1: Advanced Metal-Free Nanofillers for Polymers.

A covalent oxygen-rich C2N (CNO) network derived from metal-organic framework (HKUST-1) was innovatively synthesized by a rapid and green microwave irradiation method. This method can produce CNO multilayers efficiently, which paves a way for practical application of the nanosheets. Structural characterization and synthesis processes of CNO nanosheets were investigated to further understand the key role of HKUST-1. The as-prepared CNO has a layered feature, which theoretically favors to improve flame retardancy and mechanical performance of polymers. Desirable results were obtained as expected: the fire safety, antitensile, and impact resistance of polylactic acid (PLA) were prominently enhanced after adding CNO nanosheets, which can be attributed to the excellent dispersion and compatibility. PLA/CNO nanocomposite was self-distinguished at 2 wt % content of CNO, whereas the tensile strength was increased more than 36% compared with that of pure PLA, as well as the impact strength. This work broadens the application fields of CNO and endows it a possibility of actual application.

Construction of Bimetallic ZIF-Derived Co-Ni LDHs on the Surfaces of GO or CNTs with a Recyclable Method: Toward Reduced Toxicity of Gaseous Thermal Decomposition Products of Unsaturated Polyester Resin.

This work proposed an idea of recycling in preparing Co-Ni layered double hydroxide (LDH)-derived flame retardants. A novel and feasible method was developed to synthesize CO-Ni LDH-decorated graphene oxide (GO) and carbon nanotubes (CNTs), by sacrificing bimetal zeolitic imidazolate frameworks (ZIFs). Organic ligands that departed from ZIFs were recyclable and can be reused to synthesize ZIFs. ZIFs, as transitional objects, in situ synthesized on the surfaces of GO or CNTs directly suppressed the re-stacking of the carbides and facilitated the preparation of GO@LDHs and CNTs@LDHs. As-prepared hybrids catalytically reduced toxic CO yield during the thermal decomposition of unsaturated polyester resin (UPR). What is more, the release behaviors of aromatic compounds were also suppressed during the pyrolysis process of UPR composites. The addition of GO@LDHs and CNTs@LDHs obviously inhibited the heat release and smoke emission behaviors of the UPR matrix during combustion. Mechanical properties of the UPR matrix also improved by inclusion of the carbides derivatives. This work paved a feasible method to prepare well-dispersed carbides@Co-Ni LDH nanocomposites with a more environmentally friendly method.

DOPO-Modified Two-Dimensional Co-Based Metal-Organic Framework: Preparation and Application for Enhancing Fire Safety of Poly(lactic acid).

Co-based metal-organic framework (Co-MOF) nanosheets were successfully synthesized by the organic ligands with Schiff base structure. The laminated structure gives Co-MOF nanosheets a great advantage in the application in the flame retardant field. Meanwhile, -C═N- from Schiff base potentially provides active sites for further modification. In this work, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was used to modify Co-MOF (DOPO@Co-MOF) to further enhance its flame retardant efficiency. It is attractive that DOPO has a synergistic effect with Co-MOF on improving fire safety of poly(lactic acid) (PLA). The obvious decrease in the values of peak heat release (27%), peak smoke production (56%), and total CO yield (20%) confirmed the enhanced fire safety of PLA composites. The possible flame retardant mechanism was proposed based on characterization results. Moreover, the addition of DOPO@Co-MOF had a positive influence on the mechanical performance, including tensile properties and impact resistance. This work designed and synthesized two-dimensional MOFs with active groups. As-prepared Co-MOF with expected structure shows a novel direction of preparing MOFs for flame retardant application.

Construction of flame retardant coating on polyamide 6.6 via UV grafting of phosphorylated chitosan and sol-gel process of organo-silane.

Phosphorylated chitosan (PCS) was synthesized and grafted onto the surface of polyamide 6.6 (PA 6.6) fabrics via UV-induced grafting polymerization in order to improve the flame retardant properties. Subsequently, PCS grafted PA 6.6 fabrics were modified by (3-aminopropyl) triethoxysilane (APTES) through sol-gel process in order to form a cross-linking coating. The results obtained from the vertical burning test indicated that only the PCS grafted and simultaneously sol-gel treated fabrics could stop the melt dripping. A maximum reduction (30%) in the peak heat release rate was achieved for the PA6.6-PCS-4W-SG fabric sample. The optimal flame retardant effect was achieved for the PA6.6 fabrics treated by PCS and APTES simultaneously, which was attributed to the joint effect of thermal shielding exerted by the silica and char-forming effect derived from PCS.

Effect of cuprous oxide with different sizes on thermal and combustion behaviors of unsaturated polyester resin.

Cuprous oxide (Cu2O) as an effective catalyst has been applied to enhance the fire safety of unsaturated polyester resin (UPR), but the particle size influence on combustion behaviors has not been previously reported. Herein, the UPR/Cu2O composites (metal oxide particles with average particle-size of 10, 100, and 200nm) were successfully synthesized by thermosetting process. The effects of Cu2O with different sizes on thermostability and combustion behaviors of UPR were characterized by TGA, MCC, TG-IR, FTIR, and SSTF. The results revel that the addition of Cu2O contributes to sufficient decomposition of oxygen-containing compounds, which is beneficial to the release of nontoxic compounds. The smallest-sized Cu2O performs the excellent catalytic decomposition effect and promotes the complete combustion of UPR, which benefits the enhancement of fire safety. While the other additives retard pyrolysis process and yield more char residue, and thus the flame retardancy of UPR composites was improved. Therefore, catalysis plays a major role for smaller-sized particles during thermal decomposition of matrix, while flame retarded effect became gradual distinctly for the larger-sized additives.