Thermal properties of bulk polyimides: insights from computer modeling versus experiment.

Due to the great importance for many industrial applications it is crucial from the point of view of theoretical description to reproduce thermal properties of thermoplastic polyimides as accurate as possible in order to establish "chemical structure-physical properties" relationships of new materials. In this paper we employ differential scanning calorimetry, dilatometry, and atomistic molecular dynamics (MD) simulations to explore whether the state-of-the-art computer modeling can serve as a precise tool for probing thermal properties of polyimides with highly polar groups. For this purpose the polyimide R-BAPS based on dianhydride 1,3-bis(3',4-dicarboxyphenoxy)benzene (dianhydride R) and diamine 4,4'-bis(4''-aminophenoxy)biphenyl sulphone) (diamine BAPS) was synthesized and extensively studied. Overall, our findings show that the widely used glass-transition temperature Tg evaluated from MD simulations should be employed with great caution for verification of the polyimide computational models against experimental data: in addition to the well-known impact of the cooling rate on the glass-transition temperature, correct definition of Tg requires cooling that starts from very high temperatures (no less than 800 K for considered polyimides) and accurate evaluation of the appropriate cooling rate, otherwise the errors in the measured values of Tg become undefined. In contrast to the glass-transition temperature, the volumetric coefficient of thermal expansion (CTE) does not depend on the cooling rate in the low-temperature domain (T < Tg) so that comparison of computational and experimental values of CTE provides a much safer way for proper validation of the theoretical model when electrostatic interactions are taken into account explicitly. Remarkably, this conclusion is most likely of generic nature: we show that it also holds for the commercial polyimide EXTEM, another polyimide with a similar chemical structure.

Structure and Properties of Composite Fibers Based on Chitosan and Single-Walled Carbon Nanotubes for Peripheral Nerve Regeneration.

This study focused on a potential application of electrically conductive, biocompatible, bioresorbable fibers for tubular conduits aimed at the regeneration of peripheral nerves. The conducting, mechanical, and biological properties of composite fibers based on chitosan and single-walled carbon nanotubes were investigated in this paper. It was shown that introducing 0.5 wt.% of SWCNT into the composite fibers facilitated the formation of a denser fiber structure, resulting in improved strength (σ = 260 MPa) and elastic (E = 14 GPa) characteristics. Additionally, the composite fibers were found to be biocompatible and did not cause significant inflammation or deformation during in vivo studies. A thin layer of connective tissue formed around the fiber.

Properties of Resorbable Conduits Based on Poly(L-Lactide) Nanofibers and Chitosan Fibers for Peripheral Nerve Regeneration.

New tubular conduits have been developed for the regeneration of peripheral nerves and the repair of defects that are larger than 3 cm. The conduits consist of a combination of poly(L-lactide) nanofibers and chitosan composite fibers with chitin nanofibrils. In vitro studies were conducted to assess the biocompatibility of the conduits using human embryonic bone marrow stromal cells (FetMSCs). The studies revealed good adhesion and differentiation of the cells on the conduits just one day after cultivation. Furthermore, an in vivo study was carried out to evaluate motor-coordination disorders using the sciatic nerve functional index (SFI) assessment. The presence of chitosan monofibers and chitosan composite fibers with chitin nanofibrils in the conduit design increased the regeneration rate of the sciatic nerve, with an SFI value ranging from 76 to 83. The degree of recovery of nerve conduction was measured by the amplitude of M-response, which showed a 46% improvement. The conduit design imitates the oriented architecture of the nerve, facilitates electrical communication between the damaged nerve's ends, and promotes the direction of nerve growth, thereby increasing the regeneration rate.

Application of the Composite Fibers Based on Chitosan and Chitin Nanofibrils in Cosmetology.

Chitosan and composite fibers containing chitin nanofibrils have been developed for use in cosmetology. The tensile strength of the chitosan multifilaments is 160.6 ± 19.0 MPa, and of the composite multifilaments containing chitin, nanofibrils are 198.0 ± 18.4 MPa. Chitin nanofibrils introduced into the chitosan solution contribute to the creation of a new spatial arrangement of chitosan chains and their denser packing. The studies carried out by optical, scanning electron, and atomic force microscopy has shown that the serum, consisting of a mixture of lactic acid and sodium lactate, contains extended oriented structures-"liquid filaments". It has been also shown that a mixture of serum and composite fibers based on chitosan and chitin nanofibrils has mucoadhesive, film-forming properties. The introduction of composite fibers containing chitin nanofibrils into the serum promotes the reinforcing effect of liquid filaments, the lifting effect of the film. The obtained composition can be used in cosmetology as a skin care product.

Rheological and Mechanical Properties of Thermoplastic Crystallizable Polyimide-Based Nanocomposites Filled with Carbon Nanotubes: Computer Simulations and Experiments.

Recently, a strong structural ordering of thermoplastic semi-crystalline polyimides near single-walled carbon nanotubes (SWCNTs) was found that can enhance their mechanical properties. In this study, a comparative analysis of the results of microsecond-scale all-atom computer simulations and experimental measurements of thermoplastic semi-crystalline polyimide R-BAPB synthesized on the basis of dianhydride R (1,3-bis-(3',4-dicarboxyphenoxy) benzene) and diamine BAPB (4,4'-bis-(4″-aminophenoxy) biphenyl) near the SWCNTs on the rheological properties of nanocomposites was performed. We observe the viscosity increase in the SWCNT-filled R-BAPB in the melt state both in computer simulations and experiments. For the first time, it is proven by computer simulation that this viscosity change is related to the structural ordering of the R-BAPB in the vicinity of SWCNT but not to the formation of interchain linkage. Additionally, strong anisotropy of the rheological properties of the R-BAPB near the SWCNT surface was detected due to the polyimide chain orientation. The increase in the viscosity of the polymer in the viscous-flow state and an increase in the values of the mechanical characteristics (Young's modulus and yield peak) of the SWCNT-R-BAPB nanocomposites in the glassy state are stronger in the directions along the ordering of polymer chains close to the carbon nanofiller surface. Thus, the new experimental data obtained on the R-BAPB-based nanocomposites filled with SWCNT, being extensively compared with simulation results, confirm the idea of the influence of macromolecular ordering near the carbon nanotube on the mechanical characteristics of the composite material.

Polystyrene-Based Nanocomposites with Different Fillers: Fabrication and Mechanical Properties.

The paper presents a comprehensive analysis of the elastic properties of polystyrene-based nanocomposites filled with different types of inclusions: small spherical particles (SiO2 and Al2O3), alumosilicates (montmorillonite, halloysite natural tubules and mica), and carbon nanofillers (carbon black and multi-walled carbon nanotubes). Block samples of composites with different filler concentrations were fabricated by melt technology, and their linear and non-linear elastic properties were studied. The introduction of more rigid particles led to a more profound increase in the elastic modulus of a composite, with the highest rise of about 80% obtained with carbon fillers. Non-linear elastic moduli of composites were shown to be more sensitive to addition of filler particles to the polymer matrix than linear ones. A non-linearity modulus ßs comprising the combination of linear and non-linear elastic moduli of a material demonstrated considerable changes correlating with those of the Young's modulus. The changes in non-linear elasticity of fabricated composites were compared with parameters of bulk non-linear strain waves propagating in them. Variations of wave velocity and decay decrement correlated with the observed enhancement of materials' non-linearity.

Influence of the Introduced Chitin Nanofibrils on Biomedical Properties of Chitosan-Based Materials.

Hemorrhage occurring during and after surgery still remains one of the biggest problems in medicine. Although a large number of hemostatic products have been created, there is no universal preparation; thus, the development of new materials is an urgent task. The aim of this research is to increase hemostatic properties of chitosan by introducing chitin nanofibrils (ChNF). The blood absorbance by ChNF-containing chitosan sponges and time-until-arrest of bleeding were studied. Non-woven materials containing 0.5% of ChNF and materials without chitin were obtained. The studies of ζ-potential showed that the material containing 0.5% ChNF had relatively a high positive charge, but efficiencies of both materials for hemorrhage arrest were comparable to those of commercial hemostatic products (Surgicel and TachoComb). To investigate the interaction between the materials and living organism, histological studies and optical microscopy studies were conducted after implantation of fibers. Despite bioinertness of fibers, implantation of non-woven materials led to formation of significant granulomas.

Effect of Chitin Nanofibrils on Biocompatibility and Bioactivity of the Chitosan-Based Composite Film Matrix Intended for Tissue Engineering.

This paper discusses the mechanical and physicochemical properties of film matrices based on chitosan, as well as the possibility of optimizing these properties by adding chitin nanofibrils. It is shown that with the introduction of chitin nanofibrils as a filler, the mechanical stability of the composite materials increases. By varying the concentration of chitin nanofibrils, it is possible to obtain a spectrum of samples with different bioactive properties for the growth of human dermal fibroblasts. Film matrices based on the nanocomposite of chitosan and 5 wt % chitin nanofibrils have an optimal balance of mechanical and physicochemical properties and bioactivity in relation to the culture of human dermal fibroblasts.

Effect of chitin nanofibrils on electrospinning of chitosan-based composite nanofibers.

Electrical conductivity, surface tension and viscosity of chitosan-based composite nanofibers are reported. 20 wt.% of chitin nanofibrils introduced into a chitosan solution leads to increase in viscosity of the mixture; the effect of shear rate becomes more pronounced. This phenomenon is caused by the formation of cluster structures involving filler particles, and by orientation of chitin nanofibrils under the action of shear stresses in electromagnetic field. Presence of chitin facilitated formation of nanofibers in electric field and led to significant decrease in the amount of defects.

Wet spinning of fibers made of chitosan and chitin nanofibrils.

Biocompatible and bioresorbable composite fibers consisting of chitosan filled with anisotropic chitin nanofibrils with the length of 600-800 nm and cross section of about 11-12 nm as revealed by SEM and XRD were prepared by coagulation. Both chitin and chitosan components of the composite fibers displayed preferred orientations. Orientation of chitosan molecules induced by chitin nanocrystallites was confirmed by molecular modeling. The incorporation of 0.1-0.3 wt.% of chitin nanofibrils into chitosan matrix led to an increase in strength and Young modulus of the composite fibers.