Effect of Phytic Acid Addition on the Structure of Collagen-Hyaluronic Acid Composite Gel.

Composite collagen gels with hyaluronic acid are developed tissue-engineered structures for filling and regeneration of defects in various organs and tissues. For the first time, phytic acid was used to increase the stability and improve the mechanical properties of collagen gels with hyaluronic acid. Phytic acid is a promising cross-linker for collagen hydrogels and is a plant-derived antioxidant found in rich sources of beans, grains, and oilseeds. Phytic acid has several benefits due to its antioxidant, anticancer, and antitumor properties. In this work, studies were carried out on the kinetics of the self-assembly of collagen molecules in the presence of phytic and hyaluronic acids. It was shown that both of these acids do not lead to collagen self-assembly. Scanning electron microscopy showed that in the presence of phytic and hyaluronic acids, the collagen fibrils had a native structure, and the FTIR method confirmed the chemical cross-links between the collagen fibrils. DSC and rheological studies demonstrated that adding the phytic acid improved the stability and modulus of elasticity of the collagen gel. The presence of hyaluronic acid in the collagen gel slightly reduced the effect of phytic acid. The presence of phytic acid in the collagen gel improved the stability of the scaffold, but, after 1 week of cultivation, slightly reduced the viability of mesenchymal stromal cells cultured in the gel. The collagen type I gel with hyaluronic and phytic acids can be used to replace tissue defects, especially after the removal of cancerous tumors.

Influence of Molecular Weight on Thermal and Mechanical Properties of Carbon-Fiber-Reinforced Plastics Based on Thermoplastic Partially Crystalline Polyimide.

For the first time, a study of the influence of the molecular weight of the thermoplastic partially crystalline polyimide R-BAPB on the thermophysical and mechanical properties of carbon plastics was presented. The molecular weight of polyimide was determined using the method of light scattering and the study of the intrinsic viscosity of polyamic acid solutions. To obtain CFRPs, the uniform distribution of polyimide powder on continuous carbon fibers via electrostatic spraying and further hot calendering and pressing were applied. The study of the structure of the obtained carbon plastics via scanning electron microscopy has shown that the growth of the molecular weight of polyimide prevents the impregnation of carbon fiber with the introduced polyimide. Moreover, an increase in the molecular weight of polyimide leads to a rise in glass transition and thermal decomposition temperatures up to 590 °C, while the degree of crystallinity of CFRP falls. Nonetheless, raising the molecular weight from 22,000 to 70,000 g/mol of a binder polymer improves the interlayer fracture toughness G1C by more than five times.

Effect of Functionalization of the Polycaprolactone Film Surface on the Mechanical and Biological Properties of the Film Itself.

The lack of suitable functional groups for cell adhesion on the surface of Polycaprolactone (PCL) is one of the main limitations in order to use PCL for biomedical applications. The aim of this research is to modify the PCL film surface using arginine, via an aminolysis reaction. In this regard, after PCL films formation by casting method, they were immersed in arginine solutions of various concentration at room temperature or then heated to 40 °C and in the presence of isopropanol or without it. To assess the structure of the modified surface, its wettability, and mechanical properties, methods of measuring the contact angle and the strip tensile test were used, and to compare the degree of attachment and the rate of cell proliferation, the method of fluorescent staining of cultured cells was used. The change in protein synthesis by cells on the modified surface was assessed using Western blotting. The results obtained show that the treatment of PCL films with an aqueous solution of arginine at room temperature for 1 day increases the hydrophilicity of the surface. Wherein surface modification led to a two-fold decrease of mechanical strength and flow stress, but elongation increase by about 30% for PCL films after modification in 0.5 M aqueous arginine solution at room temperature. Moreover, cell attachment and proliferation, as well as collagen synthesis, were significantly enhanced after arginine modification. The proposed simple and effective method for modifying PCL films with arginine significantly expands the possibilities for developing biocompatible scaffolds for tissue engineering.

Selective Destruction of Soluble Polyurethaneimide as Novel Approach for Fabrication of Insoluble Polyimide Films.

Polymeric coatings and membranes with extended stability toward a wide range of organic solvents are practical for application in harsh environments; on the other hand, such stability makes their processing quite difficult. In this work, we propose a novel method for the fabrication of films based on non-soluble polymers. The film is made from the solution of block copolymer containing both soluble and insoluble blocks followed by selective decomposition of soluble blocks. To prove this concept, we synthesized copolymer [(imide)n-(polyurethane)]m, in which the imide blocks were combined with polyurethane blocks based on polycaprolactone. By selective hydrolysis of urethane blocks in the presence of acid, it was possible to obtain the insoluble polyimide film for the first time. It was shown that the combination of thermal and acid treatment allowed almost complete removal of urethane blocks from the initial copolymer chains. IR spectroscopy, TGA, DSC and DMA methods were used to study the evaluation of the structure and properties of polymeric material as a result of thermal oxidation and hydrolysis by acid. It was shown that the polymeric films obtained by controlled decomposition were not soluble in aprotic solvent, such as dimethylformamide, n-methylpyrrolidone and dimethyl sulfoxide, and showed very close similarity to the homopolymer consisting of the same imide monomer, poly-(4,4'oxydiphenylene)pyromellitimide, confirming the feasibility of the proposed concept and its perspectives for fabrication of organic solvent-resistant membranes.

Domain Structure, Thermal and Mechanical Properties of Polycaprolactone-Based Multiblock Polyurethane-Ureas under Control of Hard and Soft Segment Lengths.

A series of multiblock polyurethane-ureas (PUU) based on polycaprolactone diol (PCL) with a molecular mass of 530 or 2000 g/mol, as well as hard segments of different lengths and structures, were synthesized by the step-growth polymerization method. The chemical structure of the synthesized multiblock copolymers was confirmed by IR- and NMR-spectroscopy. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to determine the relaxation and phase transition temperatures for the entire series of the obtained PUU. The X-ray diffraction (XRD) method made it possible to identify PUU compositions in which the crystallizability of soft segments (SS) is manifested due to their sufficient length for self-organization and structuring. Visualization of the crystal structure and disordering of the stacking of SS with an increase in their molecular mobility during heating are shown using optical microscopy. The change in the size of the hard phase domains and the value of the interdomain distance depending on the PCL molecular mass, as well as the length and structure of the hard block in the synthesized PUU, were analyzed using small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS). The evolution of the domain structure upon passing through the melting and crystallization temperatures of PUU soft blocks was studied using SANS. The studies carried out made it possible to reveal the main correlations between the chemical structure of the synthesized PUU and their supramolecular organization as well as thermal and mechanical properties.

Development and Processing of New Composite Materials Based on High-Performance Semicrystalline Polyimide for Fused Filament Fabrication (FFF) and Their Biocompatibility.

Samples of composite materials based on high-performance semicrystalline polyimide R-BAPB (based on the dianhydride R: 1,3-bis-(3',4,-dicarboxyphenoxy)benzene and diamine BAPB: 4,4'-bis-(4″-aminophenoxy)diphenyl)) filled with carbon nanofibers and micron-sized discrete carbon fibers were obtained by FFF printing for the first time. The viscosity of melts of the composites based on R-BAPB, thermal, mechanical characteristics of the obtained composite samples, their internal structure, and biocompatibility were studied. Simultaneously with FFF printing, samples were obtained by injection molding. The optimal concentrations of carbon fillers in polyimide R-BAPB for their further use in FFF printing were determined. The effect of the incorporation of carbon fillers on the porosity of the printed samples was investigated. It was shown that the incorporation of carbon nanofibers reduces the porosity of the printed samples, which leads to an increase in deformation at break. Modification of polyimide with discrete carbon fibers increases the strength and Young's modulus sufficiently but decreases the deformation at break. The cytotoxicity analysis showed that the obtained composite materials are bioinert.

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.

Morphological Transformation in Polymer Composite Materials Filled with Carbon Nanoparticles: Part 2-Thermal and Mechanical Properties.

HDPE-based composite fibers filled by original and annealed carbon nanodiscs (oND and aND, respectively) were prepared by melt extrusion technology with high-temperature orientational drawing up to draw ratio DR = 8. The thermal properties of the obtained fibers were investigated by DSC and TGA methods. It was shown that the nanofillers can be influenced by high temperatures, at which the molecular mobility in the interlamellar regions became active, while the melting point and the crystallinity degree of the samples were not affected. Short- and long-term mechanical properties of the nanocomposite fibers were studied as well. Very rare mechanical testing of the knotted fibers was carried out and, as a result, a decrease of the knot strength up to 35% was detected. It was also revealed that the carbon nanodiscs do not reinforce the composite fibers and play a negative role in the creep processes, while the Young's modulus can be improved by 2 times for the oriented samples.

Morphological Transformation in Polymer Composite Materials Filled with Carbon Nanoparticles: Part 1-SEM and XRD Investigations.

HDPE-based nanocomposite fibers have been extruded from a melt and drawn up to draw ratio DR = 8. Two kinds of carbon nanodiscs (original ones and those exposed to additional annealing) have been used as fillers. Obtained nanocomposite fibers have been investigated with the help of different experimental methods: rheology, SEM and WAXS. It has been demonstrated that the annealed carbon nanodiscs possess a nucleation ability that finally leads to strong transformation of the material morphology.

Investigation of Polyetherimide Melt-Extruded Fibers Modified by Carbon Nanoparticles.

The fibers based on thermoplastic partially crystalline polyetherimide R-BAPB modified by vapor grown carbon nanofibers (VGCF) were prepared by melt extrusion, exposed to orientational drawing, and crystallized. All of the samples were examined by scanning electron microscopy, X-ray scattering, and differential scanning calorimetry to study how the carbon nanofiller influences on the internal structure and crystallization behavior of the obtained R-BAPB fibers. The mechanical properties of the composite R-BAPB fibers were also determined. It was found that VGCF nanoparticles introduced into R-BAPB polyimide can act as a nucleating agent that leads, in turn, to significant changes in the composite fibers morphology as well as thermal and mechanical characteristics. VGCF are able to improve an orientation degree of the R-BAPB macromolecules along the fiber direction, accelerate crystallization rate of the polymer, and enhance the fiber stability during crystallization process.

Phase Separation within a Thin Layer of Polymer Solution as Prompt Technique to Predict Membrane Morphology and Transport Properties.

In this work, the precipitation of a thin layer of a polymer solution was proposed to imitate the process of asymmetric membrane formation by a non-solvent induced phase separation (NIPS) technique. The phase inversion within the thin (<500 µm) and bulk (~2 cm) layer of polyamic-acid (PAA) in N-methyl-2-pyrrolidone (NMP) by using water as non-solvent was considered. It was shown that polymer films formed within the "limited" layer of polymer solution showed a good agreement with the morphology of corresponded asymmetric flat-sheet membranes even in the case of three-component casting solution (PAA/NMP/EtOH). At the same time, the polymer films formed on the interface of two bulk phases ("infinite" regime) did not fully correspond to the membrane structure. It was shown that up to 50% of NMP solvent in PAA solution can be replaced by ethanol, which can have a renewable origin. By changing the ethanol content in the casting solution, the average size of transport pores can be varied in the range of 12-80 nm, and the liquid permeance from 16.6 up to 207 kg/m2∙h∙bar. To summarize, the precipitation of polymer solution within the thin layer can be considered a prompt technique and a powerful tool for fast screening and optimization of the complex composition of casting solutions using its small quantity. Furthermore, the prediction of membrane morphology can be done without casting the membrane, further post-treatment procedures, and scanning electron microscopy (SEM) analysis.

Structure-Property Relationship of Polyetherimide Fibers Filled with Carbon Nanoparticles.

Nanocomposite fibers based on heat-resistant amorphous polyetherimide (PEI) were prepared by twin screw melt micro-extrusion. Vapor-grown carbon nanofibers (VGCFs) and single-wall carbon nanotubes (SWCNTs) were used as fillers which helped to achieve enhanced mechanical properties. The structure and mechanical properties of such nanocomposite fibers were studied. Electron microscopy and melt rheology data revealed a uniform distribution of the nanofillers throughout the volume of the fibers. Wide-angle X-ray scattering showed that the orientational drawing of the nanocomposite fibers led to an improved orientation of the filler particles along the fiber axis. VGCFs or SWCNTs increased the tensile strength and modulus (by ∼275 MPa and ∼5 GPa, respectively) in oriented nanocomposite fibers and decreased deformation at break. SWCNTs were found to be more effective reinforcers than VGCFs.

Transport Properties of Thermoplastic R-BAPB Polyimide: Molecular Dynamics Simulations and Experiment.

The present work evaluates the transport properties of thermoplastic R-BAPB polyimide based on 1,3-bis(3,3',4,4'-dicarboxyphenoxy)benzene (dianhydride R) and 4,4'-bis(4-aminophenoxy)biphenyl (diamine BAPB). Both experimental studies and molecular dynamics simulations were applied to estimate the diffusion coefficients and solubilities of various gases, such as helium (He), oxygen (O2), nitrogen (N2), and methane (CH4). The validity of the results obtained was confirmed by studying the correlation of the experimental solubilities and diffusion coefficients of He, O2, and N2 in R-BAPB, with their critical temperatures and the effective sizes of the gas molecules, respectively. The solubilities obtained in the molecular dynamics simulations are in good quantitative agreement with the experimental data. A good qualitative relationship between the simulation results and the experimental data is also observed when comparing the diffusion coefficients of the gases. Analysis of the Robeson plots shows that R-BAPB has high selectivity for He, N2, and CO2 separation from CH4, which makes it a promising polymer for developing gas-separation membranes. From this point of view, the simulation models developed and validated in the present work may be put to effective use for further investigations into the transport properties of R-BAPB polyimide and nanocomposites based on it.