Nanofibrillar Network Research Articles

In-situ understanding on the formation of fibrillar morphology in green solvent processed all-polymer solar cells

Abstract Solid additive engineering has been intensively explored on morphology tuning for highly efficient all-polymer solar cells (all-PSCs), a promising photovoltaic technology towards multi-scenario application. Although the nano-fibrillar network of the active layer induced by additive treatment is confirmed as the key factor for power conversion efficiency (PCE) of all-PSCs, its formation mechanism is not clearly revealed, for lack of precise and convincing real-time observation of crystallization and phase separation during the liquid-to-solid transition process of spin-coating. Herein we report an in-situ grazing incidence wide-angle/small-angle X-ray scattering (GIWAXS/GISAXS) screening that reveals the fact that naphthalene derived solid additives can suppress the aggregation of the polymer acceptor (PY-IT) at the beginning stage of spin coating, which provides sufficient time and space for the polymer donor (PM6) to form the fibril structure. Moreover, guided by this knowledge, a ternary all-polymer system is proposed, which achieves cutting-edge level PCEs for both small-area (0.04 cm2) (also decent operational stability) and large-area (1 cm2) devices.

Shape Memory Polymer Foam Based on Nanofibrillar Composites of Polylactide/Polyamide.

This paper presents the novel development of a shape memory polymer foam based on polymer-polymer nanocomposites. Herein, polylactide (PLA)/biosourced polyamide (PA) foams are fabricated by in situ fibrillation of polymer blends and a subsequent supercritical CO2 foaming technique. In this system, PLA serves as a shape memory polymer to endow this foam with a shape memory effect (SME), and in situ generated PA nanofibers are employed to reinforce the PLA cell walls and provide an additional permanent phase. A concentration of PA, 5 wt.%, was chosen to form an entangled nanofibrillar network. Foams of PLA/PA nanoblends with the same content of constituents were fabricated to reveal the effect of minor phase morphology on the cell structure and shape memory behavior of polymer foams. Profiting from the reinforcing effect of PA nanofibers, the PLA/PA nanocomposite foam exhibits smaller foam cells, a narrower cell size distribution and a comparable cell concentration than the PLA/PA nanoblend foam. In addition, PA nanofibers, unlike PA nanodroplets, favor the shape fixation ratio and recovery ratio and shorten the shape recovery time.

Impact of Weak Organic Acids as Coagulants on Tailoring the Properties of Cellulose Aerogel Beads.

Tailoring the properties of cellulose aerogel beads was investigated in the present study by using weak organic acids as coagulants. Three different weak acids were specifically chosen, acetic acid, lactic acid and citric acid. For comparative studies, a strong acid, hydrochloric acid was examined. The production of aerogel beads by conventional dropping technique was controlled and optimized for weak acids. Aerogels were characterized by density analyses, scanning electron microscopy, nitrogen adsorption-desorption analysis, X-ray powder diffractometry and IR spectroscopy. In common, all the aerogel beads showed interconnected nanofibrillar network, high specific surface area, high pore volume, high porosity and meso- and macroporous structure. In particular, when the weakest acid (acetic acid) was used as coagulant in the regeneration bath, the lowest shrinkage was observed. As a result, the cellulose aerogel beads produced from acetic acid showed the highest values of specific surface area (423 m2 g-1) and pore volume (3.6 cm3 g-1). The porous structure can be tuned by the choice of regeneration bath, which has either strong acid or a high concentration of weak acid. The aerogel beads were pure and showed cellulose II crystallinity. Hence this study paves an alternative path way to tailor the properties of cellulose aerogel beads.

Green Polymer Electrolytes Prepared by a Cost-Effective Approach.

The preparation of solid polymer electrolytes (SPEs) using poly(ethylene oxide) (PEO) typically involves incorporating fillers or undergoing chemical modifications to reduce crystallinity and enhance conductivity. PEO with a lower molecular weight, known as polyethylene glycol (PEG), exhibits higher conductivity, despite weaker mechanical strength. It is commonly employed as a plasticizer to improve the conductivity of SPEs or to fabricate PEG-based gel polymer electrolytes (GPEs). In this study, we use a straightforward approach to create innovative SPEs by blending liquid polymer electrolytes (LPEs), particularly low-molecular-weight polyethylene glycol (PEG), with a molecular weight of 400 g/mol, and sustainable poly(l-lactide) (PLLA). Solid PEG/PLLA forms are achieved by introducing 30 wt % of PLLA. Subsequently, the addition of lithium salts results in the development of novel PEG/PLLA SPEs. Another focal point of this study involves incorporating 1,3:2,4-dibenzylidene sorbitol (DBS) into these PEG/PLLA systems. DBS, an organic gelator derived from natural sugars, demonstrates self-assembly, leading to the formation of a nanofibrillar network structure. Leveraging DBS's ability to form organogels in liquid organic environments, we facilitate the transformation of low PLLA content LPEs into innovative solvent-free GPEs. Our prepared PEG/PLLA SPEs exhibited a maximum conductivity value of 4.39 × 10-5 S/cm, approximately five times higher than that of neat PEG (10000 g/mol) SPEs. The ionic conductivity exhibited a declining trend as the content of PLLA and DBS increased. However, there was an improvement in electrochemical stability. Furthermore, the incorporation of PLLA and DBS into electrolytes contributed to enhanced mechanical support and stability within the electrolyte layer. This, in turn, mitigated capacity decay and improved the cycling performance of assembled lithium-ion cells.

Food-grade emulsion gels and oleogels prepared by all-natural dual nanofibril system from citrus fiber and glycyrrhizic acid

The natural dual nanofibril system consisting of the rigid semicrystalline nanofibrils disintegrated from citrus fiber (CF) and soft semiflexible nanofibrils self-assembled from glycyrrhizic acid (GA) has been recently shown to be effective structural building blocks for fabrication of emulsion gels. In this work, the effect of the CF nanofibrils prepared by different mechanical disintegration approaches (i.e., high-pressure microfluidization and hydrodynamic cavitation) on the interfibrillar CF-GA interactions and the subsequent formation and properties of emulsion gels were investigated, with the aim of evaluating the potential of the dual nanofibril-stabilized emulsion gels as templates for synthesizing all-natural edible oleogels. The obtained results demonstrate that compared to the cavitation, the high-pressure microfluidization is more capable of generating CF nanofibrils with a higher degree of nanofibrillation and individualization, thus forming a denser CF-GA gel network with higher viscoelasticity and structural stability due to the stronger multiple intrafibrillar and interfibrillar interactions. The emulsion gels stabilized by the dual nanofibril system are demonstrated to be an efficient template to fabricate solid-like oleogels, and the structural properties of the oleogels can be well tuned by the mechanical disintegration of CF and the GA nanofibril concentration. The prepared oleogels possess high oil loading capacity, dense network microstructure, superior rheological and large deformation compression performances, and satisfactory thermal stability, which is attributed to the compact and ordered CF-GA dual nanofibrillar network via multiple hydrogen-bonding interactions in the continuous phase as well as at the droplet surface. This study highlights the unique use of all-natural dual nanofibrils to develop oil structured soft materials for sustainable applications.

Crystal to Hydrogel Transformation in S-Benzyl-L-Cysteine-Containing Cyclic Dipeptides - Nanostructure Elucidation and Applications.

Cyclic dipeptides (CDPs) are crucial building blocks for a range of functional nanomaterials due to their simple chemical structure and high molecular stability. In this investigation, we synthesized a set of S-benzyl-L-cysteine-based CDPs (designated as P1-P6) and thoroughly examined their self-assembly behavior in a methanol-water solvent to elucidate the relationship between their structure and gelation properties. The hydrophobicity of the amino acids within the CDPs was gradually increased. The present study employed a comprehensive array of analytical techniques, including NMR, FT-IR, AFM, thioflavin-T, congo-red CD, X-ray crystallography, and biophysical calculations like Hirshfield Surface analysis and DFT analysis. These methods revealed that in addition to hydrogen bonding, the hydrophobic nature of the amino acid side chain significantly influences the propensity of CDPs to form hydrogels. Each CDP yielded distinct nanofibrillar networks rich in β-sheet structures, showcasing unique morphological features. Moreover, we explored the practical application of these CDP-based hydrogels in water purification by utilizing them to remove harmful organic dyes from contaminated water. This application underscores the potential of CDPs in addressing environmental challenges, offering a promising avenue for the future development of these materials in water treatment technologies.

Sonication-Induced Boladipeptide-Based Metallogel as an Efficient Electrocatalyst for the Oxygen Evolution Reaction.

Bioinspired, self-assembled hybrid materials show great potential in the field of energy conversion. Here, we have prepared a sonication-induced boladipeptide (HO-YF-AA-FY-OH (PBFY); AA = Adipic acid, F = l-phenylalanine, and Y = l-tyrosine) and an anchored, self-assembled nickel-based coordinated polymeric nanohybrid hydrogel (Ni-PBFY). The morphological studies of hydrogels PBFY and Ni-PBFY exhibit nanofibrillar network structures. XPS analysis has been used to study the self-assembled coordinated polymeric hydrogel Ni-PBFY-3, with the aim of identifying its chemical makeup and electronic state. XANES and EXAFS analyses have been used to examine the local electronic structure and coordination environment of Ni-PBFY-3. The xerogel of Ni-PBFY was used to fabricate the electrodes and is utilized in the OER (oxygen evolution reaction). The native hydrogel (PBFY) contains a gelator boladipeptide of 15.33 mg (20 mmol L-1) in a final volume of 1 mL. The metallo-hydrogel (Ni-PBFY-3) is prepared by combining 15.33 mg (20 mmol L-1) of boladipeptide (PBFY) with 3 mg (13 mmol L-1) of NiCl2·6H2O metal in a final volume of 1 mL. It displays an ultralow Tafel slope of 74 mV dec-1 and a lower overpotential of 164 mV at a 10 mA cm-2 current density in a 1 M KOH electrolyte, compared to other electrocatalysts under the same experimental conditions. Furthermore, the Ni-PBFY-3 electrocatalyst has been witnessed to be highly stable during 100 h of chronopotentiometry performance. To explore the OER mechanism in an alkaline medium, a theoretical calculation was carried out by employing the first-principles-based density functional theory (DFT) method. The computed results obtained by the DFT method further confirm that the Ni-PBFY-3 electrocatalyst has a high intrinsic activity toward the OER, and the value of overpotential obtained from the present experiment agrees well with the computed value of the overpotential. The biomolecule-assisted electrocatalytic results provide a new approach for designing efficient electrocatalysts, which could have significant implications in the field of green energy conversion.

A multifunctional biogenic films and coatings from synergistic aqueous dispersion of wood-derived suberin and cellulose nanofibers

Here, biogenic and multifunctional active food coatings and packaging with UV shielding and antimicrobial properties were structured from the aqueous dispersion of an industrial byproduct, suberin, which was stabilized with amphiphilic cellulose nanofibers (CNF). The dual-functioning CNF, synthesized in a deep eutectic solvent, functioned as an efficient suberin dispersant and reinforcing agent in the packaging design. The nanofibrillar percolation network of CNF provided a steric hindrance against the coalescence of the suberin particles. The low CNF dosage of 0.5 wt% resulted in dispersion with optimal viscosity (208.70 Pa.s), enhanced stability (instability index of <0.001), and reduced particle size (9.37 ± 2.43 μm). The dispersion of suberin and CNF was further converted into self-standing films with superior UV-blocking capability, good thermal stability, improved hydrophobicity (increase in water contact angle from 61° ± 0.15 to 83° ± 5.11), and antimicrobial properties against gram-negative bacteria. Finally, the synergistic bicomponent dispersions were demonstrated as fruit coatings for bananas and packaging for strawberries to promote their self-life. The coatings and packaging considerably mitigated fruit deterioration and improved their freshness by preventing moisture loss and microbial attack. This sustainable approach is expected to pave the way toward advanced, biogenic, and active food packaging based on widely available bioresources.

Dual Self-Assembly of Puerarin and Silk Fibroin into Supramolecular Nanofibrillar Hydrogel for Infected Wound Treatment.

The treatment of infected wounds remains a challenging biomedical problem. Some bioactive small-molecule hydrogelators with unique rigid structures can self-assemble into supramolecular hydrogels for wound healing. However, they are still suffered from low structural stability and bio-functionality. Herein, a supramolecular hydrogel antibacterial dressing with a dual nanofibrillar network structure is proposed. A nanofibrillar network created by a small-molecule hydrogelator, puerarin extracted from the traditional Chinese medicine Pueraria, is interconnected with a secondary macromolecular silk fibroin nanofibrillar network induced by Ga ions via charge-induced supramolecular self-assembly. The resulting hydrogel features adequate mechanical strength for sustainable retention at wounds. Good biocompatibility and efficient bacterial inhibition are obtained when the Ga ion concentration is 0.05%. Otherwise, the substantial release of Ga ions and puerarin endows the hydrogel with excellent hemostatic and antioxidative properties. In vivo, evaluation of a mouse-infected wound model demonstrates that its healing effect outperformed that of a commercially available silver-containing wound dressing. The experimental group successfully achieves a 100% wound closure rate on day 10. This study sheds new light on the design of nanofibrillar hydrogels based on supramolecular self-assembly of naturally derived bioactive molecules as well as their clinical use for treating chronic infected wounds.

Preparation of cellulose-paraffin composite foams by an emulsion–gelation method using aqueous inorganic salt solution for thermal energy regulation

Leakage of paraffin phase-change materials during phase transitions limits their application. Cellulose is an environment-friendly material that has the potential to resolve leakage problems. In this study, large-scale, firm, and no leakage cellulose-paraffin composite foams were fabricated via an emulsion–gelation method using a cellulose/LiBr solution. Spherical paraffin particles were embedded into the three-dimensional nanofibrillar network structure of the regenerated cellulose, with no chemical interaction between the paraffin and cellulose. This cellulose-paraffin foam exhibited excellent mechanical properties, with a maximum elastic modulus value of 7.08 MPa. No leakage was observed at 80 °C even when the paraffin content was 80 %. During phase change, the maximum latent heat was 173.2 J g−1. The thermal conductivity was relatively low (46.5–77.2 mW m−1); this represented 23–38 % of the thermal conductivity of pure paraffin. Therefore, foams are promising materials for efficient and reliable thermal energy storage applications.

Construction of Nanofibrillar Networked Wood Aerogels Derived from Typical Softwood and Hardwood: A Comparative Study on the In Situ Formation Mechanism of Nanofibrillar Networks.

The construction of networks within natural wood (NW) lumens to produce porous wood aerogels (WAs) with fascinating characteristics of being lightweight, flexible, and porous is significant for the high value-added utilization of wood. Nonetheless, how wood species affect the structure and properties of WAs has not been comprehensively investigated. Herein, typical softwood of fir and hardwoods of poplar and balsa are employed to fabricate WAs with abundant nanofibrillar networks using the method of lignin removal and nanofibril's in situ regeneration. Benefiting from the avoidance of xylem ray restriction and the exposure of the cellulose framework, hardwood has a stronger tendency to form nanofibrillar networks compared to softwood. Specifically, a larger and more evenly distributed network structure is displayed in the lumens of balsa WAs (WA-3) with a low density (59 kg m-3), a high porosity (96%), and high compressive properties (strain = 40%; maximum stress = 0.42 MPa; height retention = 100%) because of the unique structure and properties of WA-3. Comparatively, the specific surface area (SSA) exhibits 25-, 27-, and 34-fold increments in the cases of fir WAs (WA-1), poplar WAs (WA-2), and WA-3. The formation of nanofibrillar networks depends on the low-density and thin cell walls of hardwood. This work offers a foundation for investigating the formation mechanisms of nanonetworks and for expanding the potential applications of WAs.

Solvent-exchange triggered hydrogen bond activation strategy toward self-adaptive strong and tough organohydrogel artificial muscle

Hydrogel actuators have aroused tremendous interests in various fields such as artificial muscles, biomedicine and wearable devices. However, hydrogel actuators face persistent challenges due to their intrinsic weak and hydrophilic networks, which result in brittle and weak mechanical properties after swelling. Here, we proposed a solvent-exchange hydrogen bond activation strategy to fabricate a highly strong and tough self-adaptive organohydrogel actuators (SOA). The glycerol releasing and water retention triggers abnormal swelling of SOA due to the cross-linking of tannic acid (TA) and polyvinyl alcohol (PVA) nanofibrillar network. After the hydrogen bond activation between PVA and TA, SOA shows a denser and porous nanofibrillar network with high tensile strength (5.4 ± 0.2 MPa), high fracture energy (134.9 ± 7.6 kJ/m2), and high toughness (18.5 ± 0.7 MJ/m3). Owing to its good processibility, an anisotropic multi-filament twisted fiber actuator that exhibits ultra-high modulus (83.5 ± 2.6 MPa) and humidity-sensitive actuation performance was developed. The proposed solvent-exchange strategy shows great potential for the rational design and fabrication of bionic strong and tough artificial muscles.

Phase-inversion Induced Co-assembly of Poly(ether imide)/Aramid Nanofibrillar Composite Separators for High-speed Lithium-metal Batteries

Li-metal batteries with high energy capacities and charging rates remain far from practical implementation, mainly due to uncontrollable Li dendrite growth. Herein, we report poly(ether imide)/aramid nanofibrillar (PEI/ANF) composite separators fabricated using the phase-inversion induced co-assembly method, which can effectively suppress dendrite growth. Phase-inversion processes facilitated the co-assembly of PEI agglomerates and self-assembled ANFs into composite nanofibrillar network structures to achieve ultrahigh bulk porosity (>95%) with controlled surface porous structures. Additionally, the unique shapes of the undulated PEI sheaths over the ANF nanofibrils promoted a high surface area of the exposed ether (C−O−C) and carbonyl (C=O) functionality with high affinity to carbonate electrolytes and Li+ and PF6− ions. The resultant films presented enhanced ionic conductivities of up to 3.30 mS cm−1, and a maximum Li+ ion transference number of 0.84. These characteristics promote the formation of compact and stable fluorine-rich solid-electrolyte interphase (SEI) layers on the Li-metal anodes and effectively suppressed Li dendrite growth under extremely high charge/discharge conditions. The Li/Li symmetric cells exhibited stable operation up to 1500 cycles with a high current density of 10 mA cm–2. Moreover, LiFePO4/Li full cells with a high cathode mass loading (6–7 mg cm–2) exhibited a capacity retention of 74.3% after 500 cycles at 10 C-rate (12.0 mA cm−2). The suggested fabrication method would serve as a novel and promising approach for separators in next-generation batteries with high energy density and high C-rate capability.

Advanced Binary Guanosine and Guanosine 5'-Monophosphate Cell-Laden Hydrogels for Soft Tissue Reconstruction by 3D Bioprinting.

Soft tissue defects or pathologies frequently necessitate the use of biomaterials that provide the volume required for subsequent vascularization and tissue formation as autrografts are not always a feasible alternative. Supramolecular hydrogels represent promising candidates because of their 3D structure, which resembles the native extracellular matrix, and their capacity to entrap and sustain living cells. Guanosine-based hydrogels have emerged as prime candidates in recent years since the nucleoside self-assembles into well-ordered structures like G-quadruplexes by coordinating K+ ions and π-π stacking, ultimately forming an extensive nanofibrillar network. However, such compositions were frequently inappropriate for 3D printing due to material spreading and low shape stability over time. Thus, the present work aimed to develop a binary cell-laden hydrogel capable of ensuring cell survival while providing enough stability to ensure scaffold biointegration during soft tissue reconstruction. For that purpose, a binary hydrogel made of guanosine and guanosine 5'-monophosphate was optimized, rat mesenchymal stem cells were entrapped, and the composition was bioprinted. To further increase stability, the printed structure was coated with hyperbranched polyethylenimine. Scanning electron microscopic studies demonstrated an extensive nanofibrillar network, indicating excellent G-quadruplex formation, and rheological analysis confirmed good printing and thixotropic qualities. Additionally, diffusion tests using fluorescein isothiocyanate labeled-dextran (70, 500, and 2000 kDa) showed that nutrients of various molecular weights may diffuse through the hydrogel scaffold. Finally, cells were evenly distributed throughout the printed scaffold, cell survival was 85% after 21 days, and lipid droplet formation was observed after 7 days under adipogenic conditions, indicating successful differentiation and proper cell functioning. To conclude, such hydrogels may enable the 3D bioprinting of customized scaffolds perfectly matching the respective soft tissue defect, thereby potentially improving the outcome of the tissue reconstruction intervention.

3D printed graphene aerogels using conductive nanofibrillar network formulation

Despite recent progress in 3D printing of graphene, formulation of aqueous 3D printable graphene inks with desired rheological properties for direct ink writing (DIW) of multifunctional graphene macrostructures remains a major challenge. In this work, we develop a novel 3D printable pristine graphene ink in aqueous phase using conductive nanofibrillar network formulation by controlling the interfacial interactions between graphene and PEDOT:PSS nanofibrils. The formulated inks, tailored for energy applications, provide excellent 3D printability for fabricating multilayer 3D structures (up to 30 layers) with spanning features and high aspect ratio. The 3D printed aerogels, comprising interconnected networks of graphene flakes and PEDOT:PSS nanofibrils, exhibit excellent electrical conductivity as high as ∼630 S m − 1 and can be converted into conductive hydrogels via swelling in water/electrolyte. The formulated graphene inks were used for fabricating 3D printed supercapacitor electrodes (power density of 11.3 kW kg−1 and energy density of 7.3 Wh kg−1) with excellent performance and durability.

Histidine-Containing Amphiphilic Peptide-Based Non-Cytotoxic Hydrogelator with Antibacterial Activity and Sustainable Drug Release.

A histidine-based amphiphilic peptide (P) has been found to form an injectable transparent hydrogel in phosphate buffer solution over a pH range from 7.0 to 8.5 with an inherent antibacterial property. It also formed a hydrogel in water at pH = 6.7. The peptide self-assembles into a nanofibrillar network structure which is characterized by high-resolution transmission electron microscopy, field-emission scanning electron microscopy, atomic force microscopy, small-angle X-ray scattering, Fourier-transform infrared spectroscopy, and wide-angle powder X-ray diffraction. The hydrogel exhibits efficient antibacterial activity against both Gram-positive bacteria Staphylococcus aureus (S. aureus) and Gram-negative bacteria Escherichia coli (E. coli). The minimum inhibitory concentration of the hydrogel ranges from 20 to 100 μg/mL. The hydrogel is capable of encapsulation of the drugs naproxen (a non-steroidal anti-inflammatory drug), amoxicillin (an antibiotic), and doxorubicin, (an anticancer drug), but, selectively and sustainably, the gel releases naproxen, 84% being released in 84 h and amoxicillin was released more or less in same manner with that of the naproxen. The hydrogel is biocompatible with HEK 293T cells as well as NIH (mouse fibroblast cell line) cells and thus has potential as a potent antibacterial and drug releasing agent. Another remarkable feature of this hydrogel is its magnification property like a convex lens.

Mixed Conductive, Injectable, and Fluorescent Supramolecular Eutectogel Composites.

Eutectogels are an emerging family of soft ionic materials alternative to ionic liquid gels and organogels, offering fresh perspectives for designing functional dynamic platforms in water-free environments. Herein, the first example of mixed ionic and electronic conducting supramolecular eutectogel compositesis reported. A fluorescent glutamic acid-derived low-molecular-weight gelator (LMWG) was found to self-assemble into nanofibrillar networks in deep eutectic solvents (DES)/ poly(3,4-ethylenedioxythiophene) (PEDOT): chondroitin sulfate dispersions. These dynamic materials displayed excellent injectability and self-healing properties, high ionic conductivity (up to 10-2 S cm-1), good biocompatibility, and fluorescence imaging ability. This set of features turns the mixed conducting supramolecular eutectogels into promising adaptive materials for bioimaging and electrostimulation applications.

Mixed Conductive, Injectable, and Fluorescent Supramolecular Eutectogel Composites

AbstractEutectogels are an emerging family of soft ionic materials alternative to ionic liquid gels and organogels, offering fresh perspectives for designing functional dynamic platforms in water‐free environments. Herein, the first example of mixed ionic and electronic conducting supramolecular eutectogel composites is reported. A fluorescent glutamic acid‐derived low‐molecular‐weight gelator (LMWG) was found to self‐assemble into nanofibrillar networks in deep eutectic solvents (DES)/poly(3,4‐ethylenedioxythiophene) (PEDOT): chondroitin sulfate dispersions. These dynamic materials displayed excellent injectability and self‐healing properties, high ionic conductivity (up to 10−2 S cm−1), good biocompatibility, and fluorescence imaging ability. This set of features turns the mixed conducting supramolecular eutectogels into promising adaptive materials for bioimaging and electrostimulation applications.

In Situ Nanofibrillar Polypropylene-Based Composite Microcellular Foams with Enhanced Mechanical and Flame-Retardant Performances

With the increasing demand for plastic components, the development of lightweight, high strength and functionalized polypropylene (PP) from a cost-effective and environmentally friendly process is critical for resource conservation. In situ fibrillation (INF) and supercritical CO2 (scCO2) foaming technology were combined in this work to fabricate PP foams. Polyethylene terephthalate (PET) and poly(diaryloxyphosphazene)(PDPP) particles were applied to fabricate in situ fibrillated PP/PET/PDPP composite foams with enhanced mechanical properties and favorable flame-retardant performance. The existence of PET nanofibrils with a diameter of 270 nm were uniformly dispersed in PP matrix and served multiple roles by tuning melt viscoelasticity for improving microcellular foaming behavior, enhancing crystallization of PP matrix and contributing to improving the uniformity of PDPP's dispersion in INF composite. Compared to pure PP foam, PP/PET(F)/PDPP foam exhibited refined cellular structures, thus the cell size of PP/PET(F)/PDPP foam was decreased from 69 to 23 μm, and the cell density increased from 5.4 × 106 to 1.8 × 108 cells/cm3. Furthermore, PP/PET(F)/PDPP foam showed remarkable mechanical properties, including a 975% increase in compressive stress, which was attributed to the physical entangled PET nanofibrils and refined cellular structure. Moreover, the presence of PET nanofibrils also improved the intrinsic flame-retardant nature of PDPP. The synergistical effect of the PET nanofibrillar network and low loading of PDPP additives inhibited the combustion process. These gathered advantages of PP/PET(F)/PDPP foam make it promising for lightweight, strong, and fire-retardant polymeric foams.

Synergistic Fluorine⋅⋅⋅Sulfur Intra‐ and Intermolecular Interactions on Dopant‐Free Hole Transport Material for Efficient and Stable Inverted Perovskite Solar Cells

Designing dopant‐free small‐molecule hole transport materials (HTMs) with self‐assembly behavior via noncovalent interactions is considered as one effective strategy to achieve high‐performance inverted perovskite solar cells (PSCs). Herein, two donor‐π bridge‐donor (D–π–D) HTMs are presented, TPASF and TPAOF, containing 3,6‐dimethoxythieno[3,2‐b]thiophene as a core part with 3‐fluoro‐N,N‐bis(4‐(methylthio)phenyl)aniline and 3‐fluoro‐N,N‐bis(4‐methoxyphenyl)aniline as side group. The synergistic F⋅⋅⋅S dipole–dipole intra‐ and intermolecular interactions in TPASF drive the self‐assembly of this molecule into a supramolecular nanofibrillar network, leading to high hole mobility, superior interfacial properties, and providing a good growth template for the perovskite layer atop. The corresponding dopant‐free TPASF‐based inverted devices exhibit a promising power conversion efficiency of 21.01% with a long T 80 lifetime of ≈632 h under operational conditions. This work paves the way for the further development of new dopant‐free self‐assembled HTM designs for highly efficient and stable inverted PSCs.