Xiaolong Jia

Effect of Matrix Molecular Weight on the Coarsening Mechanism of Polymer-Grafted Gold Nanocrystals

A systematic evaluation of the effect of polymer matrix molecular weight on the coarsening kinetics of uniformly dispersed polystyrene-grafted gold nanoparticles is presented. Particle coarsening is found to proceed via three stages (i.e., atomic-diffusion-based Ostwald ripening (OR), particle-migration-based collision-coalescence, and the subsequent reshaping of particle assemblies). The relative significance of each stage and hence the evolution of particle size and shape have been found to depend sensitively upon time, temperature, and the molecular weight of the host polymer. At temperatures close to the matrix glass-transition temperature, Ostwald ripening has been observed to be dominant on all experimental timescales. With increasing annealing temperature, collision coalescence becomes the dominant mode of coarsening, leading to rapid particle growth. The onset of the latter process is found to be increasingly delayed with increasing molecular weight of the polymer host. Particle coalescence is observed to proceed via two fundamental modes (i.e., diffusion-limited aggregation and growth resulting in the formation of fractal particle clusters and the subsequent recrystallization into more spherical monolithic aggregate structures). Interestingly, particle coarsening in high-molecular-weight matrix polymers is found to proceed significantly faster than predicted on the basis of the bulk polymer viscosity; this acceleration is interpreted to be a consequence of the network characteristics of high-molecular-weight polymers by analogy to the phenomenon of nanoviscosity that has been reported in the context of nanoparticle diffusion within high-molecular-weight polymers.

Effectively Exerting the Reinforcement of Dopamine Reduced Graphene Oxide on Epoxy-Based Composites via Strengthened Interfacial Bonding.

The effects of dopamine reduced graphene oxide (pDop-rGO) on the curing activity and mechanical properties of epoxy-based composites were evaluated. Taking advantage of self-polymerization of mussel-inspired dopamine, pDop-rGO was prepared through simultaneous functionalization and reduction of graphene oxide (GO) via polydopamine coating. Benefiting from the universal binding ability of polydopamine, good dispersion of pDop-rGO in epoxy matrix was able to be achieved as the content of pDop-rGO being below 0.2 wt %. Curing kinetics of epoxy composites with pDop-rGO were systematically studied by nonisothermal differential scanning calorimetry (DSC). Compared to the systems of neat epoxy or epoxy composites containing GO, epoxy composites loaded with pDop-rGO showed lower activation energy (Eα) over the range of cure (α). It revealed that the amino-bearing pDop-rGO was able to react with epoxy matrix and enhance the curing reactions as an amine-type curing agent. The nature of the interactions at GO-epoxy interface was further evaluated by Raman spectroscopy, confirming the occurrence of chemical bonding. The strengthened interfacial adhesion between pDop-rGO and epoxy matrix thus enhanced the effective stress transfer in the composites. Accordingly, the tensile and flexural properties of EP/pDop-rGO composites were enhanced due to both the well dispersion and strong interfacial bonding of pDop-rGO in epoxy matrix.

Numerical Characterization of Magnetically Aligned Multiwalled Carbon Nanotube–Fe3O4 Nanoparticle Complex

Alignment states of one-dimensional multiwalled carbon nanotubes containing various contents of zero-dimensional ferriferrous oxide nanoparticles (MWCNT-Fe3O4) were numerically characterized. MWCNT-Fe3O4 complexes were successfully prepared via in situ surface-initiated atom transfer radical polymerization, followed by a coprecipitation process. The complexes showed strong magnetism, which endowed them with the ability to be aligned under the action of an external magnetic field. The intensity of the magnetic field, loading content of Fe3O4 nanoparticles, and viscosity of dispersing medium, however, all had substantial effects on the alignment degree. To evaluate the alignment effectively and quantitatively, an orientation tensor description based on marking the direction of a single MWCNT in a selected region of optical images was employed. The results showed that MWCNT-Fe3O4 complex containing 26 wt % of Fe3O4 nanoparticles achieved a desirable alignment in deionized water under a magnetic field intensity of 0.10 T. Accordingly, epoxy composites reinforced with such aligned MWCNT-Fe3O4 complexes displayed 12.3 and 10.9% enhancement in tensile strength and modulus, as well as 8.9 and 6.1% enhancement in flexural strength and modulus, respectively.

Improved bioactivity of PAN-based carbon nanofibers decorated with bioglass nanoparticles

Composite nanofibers composed of polyacrylonitrile (PAN)-based carbon nanofibers and bioactive glass (BG) nanoparticles have been prepared by electrospinning and in situ sintering. Morphology observation showed that the BG nanoparticles of size 20–50 nm were uniformly distributed on the surface of composite nanofibers with 350 nm average diameter after carbonization. Biological mineralization indicated the formation of apatite-like layer on the surface of composite nanofibers, in which the composition of carbonate hydroxyapatite was proved by FTIR and XRD analysis. Cell growth dynamics according to cellular morphology, CCK-8 assay, and alkaline phosphatase activity assay exhibited better cell adhesion, proliferation, and osteogenic induction of bone marrow-derived mesenchymal stem cells cultured on the composite nanofibers, which suggested the higher bioactivity of composite nanofibers compared to pure PAN-based carbon nanofibers.

Polylactide–hydroxyapatite nanocomposites with highly improved interfacial adhesion via mussel-inspired polydopamine surface modification

The poor interfacial adhesion between organic and inorganic components remains the primary obstacle in obtaining composite scaffolds of high performance for bone tissue engineering. Mussel-inspired dopamine surface modification on inorganic components is a potential solution for this problem. Herein, hydroxyapatite (HA) nano-rods were freshly made by a co-precipitation method and subjected to polydopamine (PDA) coating. Then the modified HA nano-rods were mixed into biodegradable poly(L-lactide) (PLLA) to get PLLA/HA nanocomposites. The PDA modification was found to be mild and easy to handle, and was effective in improving the dispersibility of HA nano-rods in chloroform and especially in PLLA/chloroform solution. The resulting PLLA/HA composite films and porous scaffolds demonstrated significant enhancements in their mechanical properties at relatively high contents (30–60 wt%) of modified HA nano-rods in comparison with those composites containing unmodified HA nano-rods. This was thought to be mainly attributed to both the even distribution of modified HA nano-rods throughout the PLLA matrix and the strong interfacial adhesion between HA and PLLA components. The PLLA/HA composites displayed good biocompatibility with bone mesenchymal stem cells (BMSCs) and could enhance the osteogenic differentiation of BMSCs, indicating the PDA modification has no adverse effect on biological properties. These results confirmed the idea of using mussel-inspired dopamine surface modification as a feasible and efficient approach in developing organic–inorganic composite materials for bone regeneration studies.

Nanoporous structured carbon nanofiber–bioactive glass composites for skeletal tissue regeneration

Bioactive glass (BG) decorated nanoporous composite carbon nanofibers (PCNF-BG) were prepared for the purpose of obtaining effective substrates for skeletal tissue regeneration. The preparation was conducted by electrospinning of polyacrylonitrile (PAN)-polymethylmethacrylate (PMMA) blends with the addition of sol-gel precursors of 58s-type (mol%: 58% SiO2-38% CaO-4% P2O5) BG, followed by high temperature thermal treatment. The removal of PMMA during the carbonization of PAN generated numerous slit-like nanoporous structures along CNFs, leading to a significant enhancement in the specific surface area, surface roughness and pore volume, which was confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) characterizations. PCNF-BG composites with different specific surface areas were biologically evaluated by experiments of biomineralization in simulated body fluid (SBF), in vitro MC3T3-E1 osteoblast proliferation and osteogenic differentiation. Compared to non-porous CNF/BG, the nanoporous structure distinctively enlarged the interfacial reaction area of the BG component with a medium environment and thus enhanced the bioactivity of CNFs by accelerating the dissolution of the BG component and providing abundant nucleation sites for hydroxyapatite depositions. The released ions displayed distinct promotion in proliferation and osteogenic differentiation of osteoblast cells, which promoted the osteocompatibility of carbon-based materials significantly.

Growth mechanism of bioglass nanoparticles in polyacrylonitrile-based carbon nanofibers

Polyacrylonitrile (PAN) electrospinning in combination with sol–gel method has been a common technique to produce inorganic nanoparticles containing composite carbon nanofibers (CNFs) for diverse applications. To investigate the morphology evolution and crystal transformation of inorganic components along with CNF formation, bioactive glass (BG) containing CNFs (CNF/BG) were prepared by sintering as-spun PAN/precursor composite nanofibers in a nitrogen atmosphere at temperatures of 800, 1000 and 1200 °C. Comprehensive characterizations were performed with TEM, SEM-EDXA and XRD. For samples sintered at 800 °C, numerous BG nanoparticles were observed inside the CNFs and mainly in an amorphous state. With the sintering temperature raised to 1000 °C, a number of spherical BG nanoparticles were detected on the surface of the resulting CNFs, with a crystal structure of wollastonite (β-CaSiO3) polycrystals. When the samples were sintered at 1200 °C, the BG nanoparticles on the surface of CNFs merged into forms with cuboid-like geometry, mainly consisting of pseudowollastonite (Ca3(Si3O9)) single crystals. Based on the geometry evolution and dynamic size distribution function analyses (Ostwald ripening and Smoluchowski equations), it was concluded that the growth of BG nanoparticles conformed to the ripening mechanism at 800 °C and migration–coalescence mechanism at 1200 °C, while the process involved both ripening and migration–coalescence mechanisms at 1000 °C.

Cell studies of hybridized carbon nanofibers containing bioactive glass nanoparticles using bone mesenchymal stromal cells

Bone regeneration required suitable scaffolding materials to support the proliferation and osteogenic differentiation of bone-related cells. In this study, a kind of hybridized nanofibrous scaffold material (CNF/BG) was prepared by incorporating bioactive glass (BG) nanoparticles into carbon nanofibers (CNF) via the combination of BG sol-gel and polyacrylonitrile (PAN) electrospinning, followed by carbonization. Three types (49 s, 68 s and 86 s) of BG nanoparticles were incorporated. To understand the mechanism of CNF/BG hybrids exerting osteogenic effects, bone marrow mesenchymal stromal cells (BMSCs) were cultured directly on these hybrids (contact culture) or cultured in transwell chambers in the presence of these materials (non-contact culture). The contributions of ion release and contact effect on cell proliferation and osteogenic differentiation were able to be correlated. It was found that the ionic dissolution products had limited effect on cell proliferation, while they were able to enhance osteogenic differentiation of BMSCs in comparison with pure CNF. Differently, the proliferation and osteogenic differentiation were both significantly promoted in the contact culture. In both cases, CNF/BG(68 s) showed the strongest ability in influencing cell behaviors due to its fastest release rate of soluble silicium-relating ions. The synergistic effect of CNF and BG would make CNF/BG hybrids promising substrates for bone repairing.

Highly moisture-resistant epoxy composites: an approach based on liquid nano-reinforcement containing well-dispersed activated montmorillonite

The effects of butyl glycidyl ether (BGE) activated montmorillonites (BGE-MMTs) on moisture-resistant characteristics of epoxy-based composites were evaluated. The activated MMTs were prepared by intercalating BGE into the inter-layer surfaces of octadecyl ammonium modified MMTs (O-MMTs) under ultrasonication, and in the form of liquid nano-reinforcement. It showed advantages of low viscosity, excellent dispersibility and high chemical reactivity in the epoxy matrix. The enhancements in tensile and flexural properties of BGE-MMTs/epoxy composites confirmed the well dispersion of BGE-MMTs in epoxy matrix and the strong interfacial adhesion between the two components. More importantly, the well-dispersed BGE-MMTs in epoxy matrix led to significant enhancement in the moisture-barrier properties of epoxy composites. In comparison with that of neat epoxy, the moisture diffusion coefficient of BGE-MMTs/epoxy composites significantly decreased from 10.1 × 10−6 to 0.3 × 10−6 cm2 s−1. The enhancement in moisture-barrier properties was ascribed to the exfoliated two-dimensional lamellar structure of MMTs extending the effective penetration paths of water molecules into tortuous forms. A model concerning moisture diffusion in BGE-MMTs/epoxy composites was suggested.

Improving interfacial adhesion with epoxy matrix using hybridized carbon nanofibers containing calcium phosphate nanoparticles for bone repairing.

Hybridized carbon nanofibers containing calcium phosphate nanoparticles (CNF/CaP) were investigated as osteocompatible nanofillers for epoxy resin. The CNF/CaP was produced by electrospinning mixture solution of polyacrylonitrile and CaP precursor sol-gel, followed by preoxidation and carbonization. The continuous and long CNF/CaP was ultrasonically chopped, mixed into epoxy resin and thermo-cured. Compared to pure CNFs with similar ultrasonication treatment, the shortened CNF/CaP reinforced composites demonstrated significant enhancement in flexural properties of epoxy composites, benefiting from the improved interfacial adhesion between CNF/CaP and resin matrix. The resulting composites also displayed good biocompatibility and sustained calcium ion release, which categorized them as promising materials for bone repairing.