A Directional Strain Sensor Based on Anisotropic Microhoneycomb Cellulose Nanofiber‐Carbon Nanotube Hybrid Aerogels Prepared by Unidirectional Freeze Drying

Aerogels are one of the most popular composite reinforcement materials because of their high porosity and their continuous and homogeneous network. Most aerogels are isotropic, thus leading to isotropic composites when they are used as fillers. This fundamentally limits their applications in areas where anisotropy is needed. Here, an anisotropic microhoneycomb cellulose nanofiber‐ (CellF)‐carbon nanotube (CNT) aerogel (denoted MCCA) is reported that contains unidirectionally aligned penetrating microchannels, which is prepared by a unidirectional freeze‐drying method, using the structure‐directing function of the CellFs. Due to its anisotropic nature, MCCA‐reinforced polydimethylsilexane (denoted MCCA/PDMS) shows distinct anisotropic behavior, with the electrical conductivity and Young's modulus along the direction of penetrating microchannels being approximately twice those in the orthogonal direction. MCCA/PDMS is used to make “directional” strain sensors with electrical resistance as the output signal. They demonstrate a 92% sensitivity difference between the microchannel direction and its orthogonal direction. This approach can be used to prepare anisotropic MCCA‐based composites with other polymers for different applications.     

A Hierarchical Nanoparticle‐in‐Micropore Architecture for Enhanced Mechanosensitivity and Stretchability in Mechanochromic Electronic Skins

Biological tissues are multiresponsive and functional, and similar properties might be possible in synthetic systems by merging responsive polymers with hierarchical soft architectures. For example, mechanochromic polymers have applications in force‐responsive colorimetric sensors and soft robotics, but their integration into sensitive, multifunctional devices remains challenging. Herein, a hierarchical nanoparticle‐in‐micropore (NP‐MP) architecture in porous mechanochromic polymers, which enhances the mechanosensitivity and stretchability of mechanochromic electronic skins (e‐skins), is reported. The hierarchical NP‐MP structure results in stress‐concentration‐induced mechanochemical activation of mechanophores, significantly improving the mechanochromic sensitivity to both tensile strain and normal force (critical tensile strain: 50% and normal force: 1 N). Furthermore, the porous mechanochromic composites exhibit a reversible mechanochromism under a strain of 250%. This architecture enables a dual‐mode mechanochromic e‐skin for detecting static/dynamic forces via mechanochromism and triboelectricity. The hierarchical NP‐MP architecture provides a general platform to develop mechanochromic composites with high sensitivity and stretchability.     

Interfacial stress transfer and property mismatch in discontinuous nanofiber/nanotube composite materials

Novel nanotubes/nanofibers with high strength and stiffness did not lead to high failure strengths/strains of nanocomposite materials. Therefore, the interfacial stress transfer and possible stress singularities, arising at the interfacial ends of discontinuous nanofibers embedded in a matrix, subjected to tensile and shear loading, were investigated by finite element analysis. The effects of Young's moduli and volume fractions on interfacial stress distributions were studied. Round-ended nanofibers were proposed to remove the interfacial singular stresses, which were caused by high stiffness mismatch of the nanoscale reinforcement and the matrix. However, the normal stress induced in the nanofiber through interfacial stress transfer was still less than 2 times that in the matrix. This stress value is far below the high strength of the nanofiber. Therefore, the load transfer efficiency of discontinuous nanofibers or nanotube composites is very low. Hence, nanofibers or nanotubes in continuous forms, which also preclude the formation of singular interfacial stress zones, are recommended over discontinuous nanofibers to achieve high strengths in nanocomposite materials.     

Electrospun La₀.₈Sr₀.₂MnO₃ nanofibers for a high-temperature electrochemical carbon monoxide sensor

Lanthanum strontium manganite (La(0.8)Sr(0.2)MnO(3), LSM) nanofibers have been synthesized by the electrospinning method. The electrospun nanofibers are intact without morphological and structural changes after annealing at 1050?°C. The LSM nanofibers are employed as the sensing electrode of an electrochemical sensor with yttria-stabilized zirconia (YSZ) electrolyte for carbon monoxide detection at high temperatures over 500?°C. The electrospun nanofibers form a porous network electrode, which provides a continuous pathway for charge transport. In addition, the nanofibers possess a higher specific surface area than conventional micron-sized powders. As a result, the nanofiber electrode exhibits a higher electromotive force and better electro-catalytic activity toward CO oxidation. Therefore, the sensor with the nanofiber electrode shows a higher sensitivity, lower limit of detection and faster response to CO than a sensor with a powder electrode.     

Processing and characterization of carbon nanofiber/syndiotactic polystyrene composites in the absence and presence of liquid crystalline polymer

Syndiotactic polystyrene (s-PS)/carbon nanofiber (CNF) composites were developed through melt process in a brabender mixer and then compression moulded. Thermal properties were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), while morphologies of the composites were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The degree of polymer and nanofiber alignment was assessed using X-ray diffraction. The resistivity reduced with increase in loading of carbon nanofibers. Surface modification of the carbon nanofiber resulted in improved properties compared to as-received carbon nanofiber composites.Blending of liquid crystalline polymer (LCP A950) with s-PS/CNFs developed composites results in improved electrical and thermal properties. This improvement is ascribed to the self reinforcing tendency of LCPs due to their rigid rod-like molecular structure, which helps to concentrate and align the carbon nanofibers.     

Polyaniline nanofiber composites with amines: Novel materials for phosgene detection

Several orders of magnitude of change in resistance are observed upon chemical doping and dedoping of the conducting polymer polyaniline. This large conductivity range can be utilized to make sensitive chemical sensors. Polyaniline, in its nanofiber form, has even greater sensing capabilities due to the small fiber diameters, high surface area, and porous nanofiber network that enhances gas diffusion into the fibers. Polyaniline nanofibers have been synthesized using a rapid mixing method and dispersed in water allowing them to be easily modified with water soluble agents, making new composite materials. Polyaniline nanofiber composite materials can be used to enhance detection of analytes that unmodified polyaniline would not otherwise be able to detect. The detection mechanism involves the reaction of an additive with the analyte to generate a strong acid that is easily detected by polyaniline, resulting in orders of magnitude changes in resistance. The reaction of the additive alone with the analyte produces no electrical response, however. In this paper, an array of amine-polyaniline nanofiber composite materials is investigated for the detection of phosgene gas. The influence of environmental conditions such as humidity and temperature are examined and a detection mechanism is presented.      

Selective nanofiber deposition via electrodynamic focusing

In this paper, we demonstrate the effect of electrodynamic focusing through a gold-coated PDMS shadow mask on the selective deposition of electrospun nanofibers. Under a suitable applied voltage, the PDMS mask repels the fibers from its surface while simultaneously forcing them into micron-sized holes and onto a collecting substrate. The presented technique is simple and can be used to produce lithographic-scale nanofiber deposition using a wide range of materials.     

Synthesis and mechanical properties of interconnected carbon nanofiber network reinforced polydimethylsiloxane composites

Carbon nanofiber (CNF) reinforced elastomer composites with light weight, sustainability of large deformation, chemical stability, corrosion and fatigue resistance, and vibration and noise reduction capability can have positive impact on a wide range of applications. However, this type of composite is still a under studied research area due to the difficulties in material handling and processing. To improve processing control and reproducibility for large scale engineering applications, cost effective carbon nanofibers (CNFs) in form of interconnected porous network structure were used as nanofillers. Processing, microstructure and mechanical properties of carbon nanofibers reinforced polydimethylsiloxane (PDMS) have been studied. Mechanical measurements on the composites show that the CNF-PDMS interfacial bonding can be until failure, interfacial debonding happens in the CNF-PDMS composites and the resulted permanent deformation stabilizes with increasing load-unload cycles with significant energy dissipation.     

Biomass‐Derived Nitrogen‐Doped Carbon Nanofiber Network: A Facile Template for Decoration of Ultrathin Nickel‐Cobalt Layered Double Hydroxide Nanosheets as High‐Performance Asymmetric Supercapacitor Electrode

The development of biomass‐based energy storage devices is an emerging trend to reduce the ever‐increasing consumption of non‐renewable resources. Here, nitrogen‐doped carbonized bacterial cellulose (CBC‐N) nanofibers are obtained by one‐step carbonization of polyaniline coated bacterial cellulose (BC) nanofibers, which not only display excellent capacitive performance as the supercapacitor electrode, but also act as 3D bio‐template for further deposition of ultrathin nickel‐cobalt layered double hydroxide (Ni‐Co LDH) nanosheets. The as‐obtained CBC‐N@LDH composite electrodes exhibit significantly enhanced specific capacitance (1949.5 F g^?1 at a discharge current density of 1 A g^?1, based on active materials), high capacitance retention of 54.7% even at a high discharge current density of 10 A g^?1 and excellent cycling stability of 74.4% retention after 5000 cycles. Furthermore, asymmetric supercapacitors (ASCs) are constructed using CBC‐N@LDH composites as positive electrode materials and CBC‐N nanofibers as negative electrode materials. By virtue of the intrinsic pseudocapacitive characteristics of CBC‐N@LDH composites and 3D nitrogen‐doped carbon nanofiber networks, the developed ASC exhibits high energy density of 36.3 Wh kg^?1 at the power density of 800.2 W kg^?1. Therefore, this work presents a novel protocol for the large‐scale production of biomass‐derived high‐performance electrode materials in practical supercapacitor applications.     

Polypyrrole/poly(vinyl alcohol-co-ethylene) nanofiber composites on polyethylene terephthalate substrate as flexible electric heating elements

Polypyrrole/poly(vinyl alcohol-co-ethylene) (PPy/PVA-co-PE) nanofiber composites on polyethylene terephthalate (PET) substrates were prepared using spray coating technique and in situ polymerization process. The electric heating behaviors of composites were investigated as functions of the amounts of nanofiber and PPy. It was observed that, the electrical resistivity of composites decreased significantly with increasing nanofiber and PPy contents. Scanning electron microscope images and infrared spectrum studies confirmed the formation of well dispersed network-like structure of PPy/PVA-co-PE nanofibers on PET substrate. Furthermore, maximum temperature attained at a given applied voltage for the composites could be well controlled by changing nanofibers and PPy amounts. PPy/PVA-co-PE nanofiber/PET composites exhibited excellent electric heating performance in aspects of rapid temperature response, long retaining behavior, thermal and operational stability. The incorporation of PPy on PVA-co-PE nanofibers/PET nonwoven substrates resulted in high conductivity and enhanced heating behavior, which have potential to be used as efficient electric heating elements.     

Dynamic Coordination of Eu–Iminodiacetate to Control Fluorochromic Response of Polymer Hydrogels to Multistimuli

New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light‐emitting materials. A new design of Eu‐containing polymer hydrogels showing fast self‐healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu–iminodiacetate (IDA) coordination in a hydrophilic poly(N,N‐dimethylacrylamide) matrix. Dynamic metal–ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self‐healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol–gel transition through the reversible formation and dissociation of Eu–IDA complexes upon various stimuli. It is demonstrated that Eu‐containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required.     

Improved fire retardancy of thermoset composites modified with carbon nanofibers

Multifunctional thermoset composites were made from polyester resin, glass fiber mats and carbon nanofiber sheets (CNS). Their flaming behavior was investigated with cone calorimeter under well-controlled combustion conditions. The heat release rate was lowered by pre-planting carbon nanofiber sheets on the sample surface with the total fiber content of only 0.38 wt.%. Electron microscopy showed that carbon nanofiber sheet was partly burned and charred materials were formed on the combusting surface. Both the nanofibers and charred materials acted as an excellent insulator and/or mass transport barrier, improving the fire retardancy of the composite. This behavior agrees well with the general mechanism of fire retardancy in various nanoparticle-thermoplastic composites.     

Electrically Conductive Carbon Nanofiber Composites with High-Density Polyethylene and Glass Fibers

Carbon nanofibers are being investigated for incorporation into composites to improve mechanical, thermal, and electrical properties. The difficulties in making such composites are issues of dispersion of the nanofiber and wetting of the nanofibers by the matrix. The processing methods developed to date tend to be complex, involving multiple steps. This paper reports on a study to make electrically conductive composites with small volume fraction of vapor-grown carbon nanofibers (VGCF). The matrix is a high-density polyethylene (HDPE); the effect of adding glass fibers to this composite is also studied. Certain types of the VGCF fibers did not produce conductive composites with standard mixing techniques; however, VGCF nanofibers heat treated with a post-processing surface treatment produced conductive composites without extensive or vigorous dispersion techniques. The results indicate that surface treatments and dispersion methods are important factors in producing conductive composites. It is demonstrated that small volume fractions of nanofiber can be used to produce conductive composites without extensive processing steps.     

Visualization and Quantitative Detection of Friction Force by Self‐Organized Organic Layered Composites

Visualization and quantitative detection of external stimuli are significant challenges in materials science. Quantitative detection of friction force, a mechanical stress, is not easily achieved using conventional stimuli‐responsive materials. Here, the quantitative detection of friction force is reported, such as the strength and accumulated ammount, from the visible color of organic layered composites consisting of polydiacetylene (PDA) and organic amines without an excitation light source. The composites of the layered diacetylene monomer crystal and interlayer organic amine are synthesized through self‐organization from the precursor solution. After topochemical polymerization, the layered composites based on PDA show tunable temperature‐responsive and mechanoresponsive color‐change properties depending on the types of interlayer amines. The layered composites are homogeneously coated on a filter paper. The change in color of the paper is quantitatively used to visualize the strength and accumulated amount of the applied friction force. Furthermore, writing pressure is measured by friction force using the paper device.     

PCL Nanopillars Versus Nanofibers: A Contrast in Progenitor Cell Morphology,Proliferation, and Fate Determination

The role of nanotopography on the long‐term response of progenitor cells is explored using polycaprolactone (PCL) nanopillar and nanofiber surfaces seeded with plastic‐adherent rat multipotent mesenchymal stromal cells (MSCs). After 4 weeks in culture under normal expansion media conditions, MSCs cultured on nanofibers exhibit better adherence, increased proliferation, and maintain increasingly dense fibroblast‐like morphologies. In contrast, MSCs seeded on nanopillar surfaces display lowered adherence, reduced proliferation, and adopt highly elongated cellular morphologies. Immunofluorescent staining of MSCs on PCL nanopillars reveals the presence of two bone marker proteins, osteopontin and osteocalcin, providing evidence for surface induced differentiation into osteoblast‐like cells. Unlike the nanopillar topography, MSCs cultured on nanofiber and smooth PCL surfaces did not appear to undergo osteogenesis. Observed differences in cellular response to the PCL nanotopographies offer strategies to direct progenitor cell populations solely based upon submicron surface modifications. This study provides a foundation for future work exploring variations in PCL nanopillar topography with the goal of optimizing adherence and osteogenic response of MSCs.     

Alkylated graphene nanosheet composites with polyaniline nanofibers

We demonstrate a simple method to prepare alkylated graphene/polyaniline composites (a-GR/PANI) using solution mixing of exfoliated alkyl Iodododecane treated graphene oxide sheets with polyaniline nanofiber; polyaniline nanofibers (PANI) prepared by using rapid mixing polymerization significantly improve the processibility of polyaniline and its performance in many conventional applications. Also, polyaniline nanofibers exhibit excellent water dispersibility due to their uniform nanofiber morphology. Morphological study using SEM and TEM analysis showed that the fibrous PANI in the composites a-GR/PANI mainly adsorbed onto the surface or intercalated between the graphene sheets, due especially to the good interfacial interaction between the alkylated gaphene and the polyaniline nanofibers. The existence of polyaniline nanofibers on the surface of the garphene and the alkylated graphene sheets was confirmed by using FT-IR, FT-Raman and X-ray diffraction analysis. Due to the good interfacial interaction between the alkylated graphene and the polyanilines nanofibers, the composite (a-GR/PANI) exhibited excellent dispersion stability in DMF compared to the same composite (GR/PANI) without alkylation. The electrical conductivity of the (GR/PANI) composite was 9% higher than that of pure PANI and the same weight percent for the composite after alkylation was 13% higher than that of pure PANI nanofibers.     

Improved fire retardancy of thermoset composites modified with carbon nanofibers

Abstract

Multifunctional thermoset composites were made from polyester resin, glass fiber mats and carbon nanofiber sheets (CNS). Their flaming behavior was investigated with cone calorimeter under well-controlled combustion conditions. The heat release rate was lowered by pre-planting carbon nanofiber sheets on the sample surface with the total fiber content of only 0.38 wt.%. Electron microscopy showed that carbon nanofiber sheet was partly burned and charred materials were formed on the combusting surface. Both the nanofibers and charred materials acted as an excellent insulator and/or mass transport barrier, improving the fire retardancy of the composite. This behavior agrees well with the general mechanism of fire retardancy in various nanoparticle-thermoplastic composites.     

Fabrication of Nanofiber Reinforced Protein Structures For Tissue Engineering

Extracellular matrices and degradable nanofibers are two very promising materials in the field of tissue engineering; however both of these structures face limitations as tissue engineering scaffolds. Extracellular matrices, such as collagen, gelatin, and laminin, have excellent biocompatibility and allow cell in growth and survival, but structural weakness makes them difficult to handle and greatly limits their uses. Degradable nanofibers support cell attachment and can provide structural support and directional guidance, but individual degradable nanofibers are fragile and have a tendency to form dense fiber bundles which limit cell penetration into the spaces between the nanofibers, especially in the case of aligned nanofibers. To overcome these difficulties, degradable loose nanofibers were embedded in protein matrix in an attempt to fabricate a hybrid scaffold with improved properties, such as improved strength, guidance, spacing among nanofibers, etc. Polycaprolactone (PCL) was used as a model material for degradable nanofibers. Gelatin was employed as a model protein for matrix structure formation. Thin hybrid films (average thickness = 2.78 um) were fabricated by wetting the loose aligned undirectional nanofiber arrays or loose aligned bi-directional nanofiber grids with a gelatin aqueous solution, which also allows for live cell loading into the nanofiber-protein composite if cell are premixed with protein solution or on the surface of the films. Gelatin film alone without nanofiber reinforcement is difficult to handle due to the weakness of the thin membrane. Gelatin films with a fiber density as low as 3% v/v were structurally robust enough for handling, and manipulation into complex shapes. Mechanical testing confirmed that the addition of nanofibers enhanced the strength of gelatin films, in both dry and hydrated state. In vitro testing confirmed that nanofiber reinforced films were biocompatible and provided cells with directional guidance. Results demonstrate the promise of gelatin/PCL nanofiber composites as a tissue scaffolding material.     

Water‐Rich Biomimetic Composites with Abiotic Self‐Organizing Nanofiber Network

Load‐bearing soft tissues, e.g., cartilage, ligaments, and blood vessels, are made predominantly from water (65–90%) which is essential for nutrient transport to cells. Yet, they display amazing stiffness, toughness, strength, and deformability attributed to the reconfigurable 3D network from stiff collagen nanofibers and flexible proteoglycans. Existing hydrogels and composites partially achieve some of the mechanical properties of natural soft tissues, but at the expense of water content. Concurrently, water‐rich biomedical polymers are elastic but weak. Here, biomimetic composites from aramid nanofibers interlaced with poly(vinyl alcohol), with water contents of as high as 70–92%, are reported. With tensile moduli of ≈9.1 MPa, ultimate tensile strains of ≈325%, compressive strengths of ≈26 MPa, and fracture toughness of as high as ≈9200 J m^?2, their mechanical properties match or exceed those of prototype tissues, e.g., cartilage. Furthermore, with reconfigurable, noncovalent interactions at nanomaterial interfaces, the composite nanofiber network can adapt itself under stress, enabling abiotic soft tissue with multiscale self‐organization for effective load bearing and energy dissipation.     

Preparation of LaFeO3 nanofibers by electrospinning for gas sensors with fast response and recovery

LaFeO(3) nanofibers are successfully prepared by the electrospinning method. XRD patterns show that the materials belong to a cubic system. After calcination at 600?°C for 3 h, SEM photographs show that the diameters of the nanofibers are about 80-90 nm and their surfaces are smooth. The response-recovery properties of an LaFeO(3) nanofiber sensor to ethanol are better than those of an LaFeO(3) nanobelt and nanoparticle sensor. LaFeO(3) nanofibers have relatively low resistance, and they improve the weakness of LaFeO(3) nanoparticles upon application. An LaFeO(3) nanofiber sensor also has good reversibility and selectivity to ethanol and is a very good p-type semiconductor material.