Construction of Polar Functional Groups on the Surface of a High-Modulus Carbon Fiber and Its Effect on the Interfacial Properties of Composites.

The interfacial bonding between carbon fibers and the resin matrix affects the mechanical properties of carbon fibers, and the increase of modulus brings a challenge to the interfacial properties of carbon fibers. The traditional anodic oxidation with ammonium bicarbonate as an electrolyte has a limited effect on the surface treatment for high-modulus carbon fibers. In this paper, anodic oxidation with an acidic electrolyte is used to treat high-modulus carbon fibers. The influence mechanism of a graphitized structure on the anodizing reaction of the carbon fiber surface was studied. Raman spectroscopy, XPS, scanning electron microscopy, dynamic contact angle, and micro-debonding were used to characterize the effect of surface treatment and its influence on interfacial properties. The results show that with a certain concentration of sulfuric acid as an electrolyte, the oxidation of the carbon fiber surface with high modulus occurs more on the graphite boundary defects. Carbonylation occurs mainly in carbon fibers with high modulus. The surface of the carbon fiber with a relatively low modulus is mainly hydroxylated and carboxylated. The surface energy and interfacial properties of high-modulus carbon fibers were improved effectively by anodic oxidation with sulfuric acid as an electrolyte. Under the condition that the mechanical properties of carbon fibers are not decreased, the surface energy of high-modulus carbon fibers with 352 GPa increases from 36.17 to 45.41 mN/m, and the interfacial shear strength (IFSS) with the epoxy resin increases by 80.8% from 34.9 to 63.1 MPa. When the fiber modulus is 455 GPa, the surface energy of the carbon fiber increases from 32.32 to 43.73 mN/m, and IFSS increases by 253.4% from 11.8 to 41.7 MPa.

Structure and Dielectric Properties of TPU Composite Filled with CNTs@PDA Nanofibers and MXene Nanosheets.

Thermoplastic polyurethane (TPU) is a kind of dielectric elastomer (DE) which can behave as an actuator, altering thickness strain in response to electrical stimulation. The composites are made up of fillers with a very high dielectric constant that are spread in a polymer matrix. It is very difficult to obtain large deformation at low voltage. In this study, we made two-dimensional (2D) MXene nanosheets with excellent conductivity and one-dimensional (1D) polydopamine (PDA)-modified CNT fiber fillers. After that, TPU dielectric elastomer films made of MXene/CNTs or MXene/CNTs@PDA were prepared. The results showed that the dielectric constant and dielectric loss of TPU dielectric film including MXene/CNTs were much higher than that containing MXene/CNTs@PDA, although Young's modulus and breakdown strength (Eb) were significantly lower. At the same time, these two types of dielectric films had a significantly higher dielectric constant and dielectric loss than pure TPU dielectric film, and their breakdown strength was significantly lower. The compatibility of CNTs@PDA fibers with the TPU matrix improves after PDA modification, and the dispersion of CNTs@PDA fibers improves, resulting in an increase in Young's modulus. MXene with a two-dimensional nanosheet structure increases the breakdown strength of the TPU dielectric elastomer under the condition of the addition of a tiny quantity. To summarize, the dielectric constant, dielectric loss, Young's modulus, and dielectric elastomer breakdown strength are mutually restrictive conditions, and the relationship between all parties must be balanced to obtain obvious deformation properties.

Electrode Potential Regulation of Carbon Fiber Based on Galvanic Coupling and Its Application in Electrochemical Grafting.

The reaction behavior of carbon fiber in electrochemical grafting is related to its electrode potential. In this paper, carbon fiber and metals with different electrode potentials were used to form combined electrodes to regulate the electrode potential of carbon fiber. The results showed that galvanic coupling was formed in the combined anode when the potential difference between carbon fiber and the metal (Δϕ = ϕCF0 - ϕmetal) was higher than 0.05 V. The electrode potential of carbon fiber was reduced due to cathodic polarization. The electrode potential of carbon fiber after galvanic coupling was proportional to the self-corrosion potential of metals. By applying the electrode potential regulation of carbon fiber in the electrochemical grafting of poly(glycidyl methacrylate) onto the carbon fiber surface, the grafting effect was significantly improved with the decrease of the electrode potential of carbon fibers. The grafting amount of carbon fibers increased from 0.83 to 69.86% as the electrode potential of carbon fibers dropped from 0.55 to -0.72 V. Consequently, the interfacial shear strength of the carbon fiber composite was remarkably promoted from 47.59 to 81.41 MPa, increasing by 71.07%.

Thermal Analysis and Crystal Structure of Poly(Acrylonitrile-Co-Itaconic Acid) Copolymers Synthesized in Water.

The composition and structure of polyacrylonitrile (PAN) precursors play an important role during thermal stabilization, which influences the properties of the resulting carbon fibers. In this paper, PAN homopolymer and PAN-itaconic (IA) copolymers with different IA contents were synthesized by aqueous phase precipitation polymerization. The effects of IA content on the structure and thermal properties were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The morphology of PAN polymers showed that the average size of the PAN particles increased with the increase of IA content in the feed. The content of the IA comonomer on the copolymers was quantitatively characterized by the relative absorbance intensity (A1735/A2243) in FTIR spectrum. With the increase of IA content in the feed, PAN-IA copolymers exhibited lower degree of crystallinity and crystal size than the control PAN homopolymer. The results from DSC curves indicated that PAN-IA1.0 copolymers had lower initial exothermic temperature (192.4 °C) and velocity of evolving heat (6.33 J g-1 °C-1) in comparison with PAN homopolymer (Ti = 238.1 °C and ΔH/ΔT = 34.6 J g-1 °C-1) in an air atmosphere. TGA results suggested that PAN-IA1.0 copolymers had higher thermal stability than PAN homopolymer, which can form a ladder structure easier during thermal processing. Therefore, PAN-IA1.0 copolymers would be a suitable candidate for preparing high performance PAN based carbon fibers.

Electrochemical grafting of poly(glycidyl methacrylate) on a carbon-fibre surface.

In this work, glycidyl methacrylate (GMA) was polymerised and grafted onto the surface of carbon fiber (CF) by using electrochemical grafting to improve the interfacial properties between the fibre and epoxy resin. The optimised conditions for electrochemical grafting and the reaction mechanism were also investigated. Results showed that GMA was covalently grafted to the CF surface by the assistance of aluminium chloride, which is a good electrolyte for electrochemical grafting. The GMA grafting ratio on the CF surface increased with electrolyte concentration and reaction time, and an optimal current intensity for the electropolymerisation was determined. On the basis of the strong correlation between the grafting ratio and the carboxyl content in the CF, a two-step mechanism of electrochemical grafting on the CF surface was proposed: first, the surface of CF was anodised to produce oxygen-containing functional groups, mainly including COOH, OH and C[double bond, length as m-dash]O. Next, when CF was used as the anode in the electrical grafting reaction, the COOH on the surface of CF would lose electrons and then remove carbon dioxide to generate carbon radicals on the surface of CF. The carbon radical would attack the carbon-carbon double bond in GMA to initiate the radical polymerisation of GMA monomers and graft polymers would be formed on the CF surface. Compared with untreated CF, the interfacial shear strength (IFSS) test proved the improvement of the interface adhesion of the modified carbon fibre (mCF) composites. This work provided a controllable electrochemical approach that could simply and quickly graft poly(glycidyl methacrylate) (PGMA) on the surface of CF.

The Structure and Properties of Polyacrylonitrile Nascent Composite Fibers with Grafted Multi Walled Carbon Nanotubes Prepared by Wet Spinning Method.

Polyacrylonitrile (PAN) grafted amino-functionalized multi walled carbon nanotubes (amino-MWCNTs) were synthesized by in situ polymerization under aqueous solvent. The grafted MWCNT/PAN nascent composite fibers were prepared by the wet spinning method. Fourier transform infrared spectroscopy and Raman spectroscopy indicated that the amino-MWCNTs and PAN macromolecular chains had interfacial interactions and formed chemical bonds. The grafting content of the PAN polymer on the amino-MWCNTs was up to 73.2% by thermo gravimetric analysis. The incorporation of the grafted MWCNTs improved the degree of crystallization and crystal size of PAN nascent fibers, and changed the thermal properties during exothermic processing in an air atmosphere. Morphology analysis and testing of mechanical properties showed that the grafted MWCNT/PAN nascent composite fibers with a more uniform diameter distribution and larger diameter had higher tensile strength and tensile modulus than the control PAN nascent fibers.

High Modulus Conductive Hydrogels Enhance In Vitro Maturation and Contractile Function of Primary Cardiomyocytes for Uses in Drug Screening.

Effective and quick screening and cardiotoxicity assessment are very crucial for drug development. Here, a novel composite hydrogel composed of carbon fibers (CFs) with high conductivity and modulus with polyvinyl alcohol (PVA) is reported. The conductivity of the composite hydrogel PVA/CFs is similar to that of natural heart tissue, and the elastic modulus is close to that of natural heart tissue during systole, due to the incorporation of CFs. PVA/CFs remarkably enhance the maturation of neonatal rat cardiomyocytes (NRCM) in vitro by upregulating the expression of α-actinin, troponin T, and connexin-43, activating the signaling pathway of α5 and ß1 integrin-dependent ILK/p-AKT, and increasing the level of RhoA and hypoxia-inducible factor-1α. As a result, the engineered cell sheet-like constructs NRCM@PVA/CFs display much more synchronous, stable, and robust beating behavior than NRCM@PVA. When exposed to doxorubicin or isoprenaline, NRCM@PVA/CFs can retain effective beating for much longer time or change the contractile rate much faster than NRCM@PVA, respectively, therefore representing a promising heart-like platform for in vitro drug screening and cardiotoxicity assessment.

Rheological Behavior of Amino-Functionalized Multi-Walled Carbon Nanotube/Polyacrylonitrile Concentrated Solutions and Crystal Structure of Composite Fibers.

The rheological behavior of amino-functionalized multi-walled carbon nanotubes (amino-CNTs)/polyacrylonitrile (PAN) concentrated solutions in the dimethyl sulphoxide solvent and the effects of the amino-CNTs on the PAN precursor fibers by wet-spinning method were investigated. The amino-CNT/PAN concentrated solutions prepared by in situ solution polymerization with homogeneous dispersion of amino-CNTs have higher complex viscosity, storage modulus and loss modulus as compared to the control PAN concentrated solutions containing 22% PAN polymer by mass. The composite fibers with amino-CNTs of 1 wt % have lower degree of crystallization, crystal size and crystal region orientation compared to the control PAN precursor fibers. However, the amino-CNT/PAN composite fibers with diameter of about 10.5 µm exhibit higher mechanical properties than the control PAN precursor fibers with diameter of about 8.0 µm. Differential scanning calorimetry analysis demonstrated that the cyclization reaction in composite fibers have broad exothermic temperature range and low exothermic rate. These results indicate that the addition of amino-CNTs into PAN precursor fibers is beneficial to controlling the process of thermal stabilization and obtaining the higher performance of composite fibers.

Effects of Amino-Functionalized Carbon Nanotubes on the Crystal Structure and Thermal Properties of Polyacrylonitrile Homopolymer Microspheres.

Amino-functionalized multi-walled carbon nanotube (amino-CNT)/polyacrylonitrile (PAN) microspheres with diameter of about 300⁻400 nm were prepared by in situ polymerization under aqueous solution. The morphology, crystal structure, and thermal properties of amino-CNTs on a PAN homopolymer were investigated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectra, X-ray diffraction, and differential scanning calorimetry. The results showed that the amino-CNTs had a significant influence on the morphology of microspheres, and the PAN matrix were grafted onto the surface of amino-CNTs with interfacial bonding between them. The XRD studies showed that the crystal size of amino-CNT/PAN microspheres with lower crystallinity was bigger than in the control PAN homopolymer. The analysis of thermal properties indicated that the amino-CNT/PAN microspheres with lower glass transition temperature had a lower initial temperature and velocity of evolving heat during the exothermic processing as compared with the PAN homopolymer. These results suggested that the incorporation of amino-CNTs into the PAN homopolymer matrix was beneficial for controlling the heat released during the stabilization processing.

Study on structure and thermal stability properties of lignin during thermostabilization and carbonization.

Soda lignin was first thermostabilized prior to carbonization. The composition, structures and thermal properties of treated lignin were investigated by EA, TGA-MS, (13)C NMR, TGA, and Raman. EA and TGA-MS results showed that the hydrogen content decreased continuously and the oxygen content increased up to 260 °C then decreased and the carbon content increased passively during thermostabilization. (13)C NMR results revealed that thermostabilization could be divided into three stages according to the evolution of the oxygenated structures content: <260 °C, 260-290 °C, >290 °C. Raman analysis showed that R values at each carbonization temperature were concave-down and non-symmetrical parabolic type and the 260 °C thermostabilized lignin after 1400 °C carbonized obtained the minimum R value 1.84. TGA results indicated that overall yields reflecting thermal stability of the thermostabilized samples, especially thermostabilized at 260-290 °C, were higher than that of untreated lignin.

Using single-walled carbon nanotubes nonwoven films as scaffolds to enhance long-term cell proliferation in vitro.

Carbon nanotubes have attracted intensive interests in biomedical research in recent years. In this study, a novel type of carbon nanotubes material so called nonwoven single-walled carbon nanotubes (SWNTs) with nanotopographic structure and macroscopic volume was used as cell growing scaffold. The morphology and surface chemistry of nonwoven SWNTs were observed and characterized through scanning electron microscopy and X-ray photoelectron spectroscopy, respectively. The cells were cultivated in nonwoven SWNTs and in other types of substrate as control. The cells growth behaviors including adhesion, proliferation, and cytoskeletal development was investigated by using cell viability assay and confocal observation. The experimental results indicated that nonwoven SWNTs exhibited significant enhancement to the cells adhesion and proliferation in at least 3 weeks. Numerous and highly organized cytoskeletal structures were observed when the cells were cultured in nonwoven SWNTs. Furthermore, an obvious promotional influence of the cells cultivated in nonwoven SWNTs scaffold upon the proliferation of those growing in the other kind of substrate through cell-cell communication had been found. The results obtained in this work are of significance to in vitro cell amplification in large scale, tissue regeneration, or guided repair, as well as biomedical device application.

Spectroscopic studies of the interaction between quercetin and G-quadruplex DNA.

Quercetin is a kind of flavonoid which has been proved to exhibit anti-tumor activity. The interaction modes of quercetins with monomeric and dimeric G-quadruplexes were studied by absorption, fluorescence, CD, and (1)H NMR spectroscopies. The ligands were found to be stacked with terminal tetrads of monomeric G-quadruplexes by intercalation and bound to dimeric G-quadruplexes by groove binding.

[Development and applications of dendrimers in biomedicine].

Dendrimers are new macromolecules synthesized in recent years, which are of great interests in many fields where they have potential important applications because of their hyperbranched, well defined and monodisperse structures. In this paper, the unique structures, general synthesis routes and basic physical and chemical properties of dendrimers are introduced in brief, and the progress in the research of dendrimers in drug (gene) delivery, contrast agents, cancer therapy were reviewed, as well as the perspective in research and applications.