Structure of Composite Based on Polyheteroarylene Matrix and ZrO2 Nanostars Investigated by Quantitative Nanomechanical Mapping

It is known that structure of the interface between inorganic nanoparticles and polymers significantly influences properties of a polymer–inorganic composite. At the same time, amount of experimental researches on the structure and properties of material near the inorganic-polymer interface is low. In this work, we report for the first time the investigation of nanomechanical properties and maps of adhesion of material near the inorganic-polymer interface for the polyheteroarylene nanocomposites based on semi-crystalline poly[4,4′-bis (4″-aminophenoxy)diphenyl]imide 1,3-bis (3′,4-dicarboxyphenoxy) benzene, modified by ZrO2 nanostars. Experiments were conducted using quantitative nanomechanical mapping (QNM) mode of atomic force microscopy (AFM) at the surface areas where holes were formed after falling out of inorganic particles. It was found that adhesion of AFM cantilever to the polymer surface is higher inside the hole than outside. This can be attributed to the presence of polar groups near ZrO2 nanoparticle. QNM measurements revealed that polymer matrix has increased rigidity in the vicinity of the nanoparticles. Influence of ZrO2 nanoparticles on the structure and thermal properties of semi-crystalline polyheteroarylene matrix was studied with wide-angle X-ray scattering, scanning electron microscopy, and differential scanning calorimetry.Russian Science Foundation, grant 16-13-1016

Characterization of Multiblock (Segmented) Copolyurethane- Imides and Nanocomposites Based Thereof Using AFM, Nanotribology, and Nanoindentation Methods

This chapter reviews our results on the morphology, tribological, and local mechanical property investigations of new copoly(urethane-imide)s (coPUIs) and nanocomposites based thereof using atomic force microscopy (AFM) and nanoindentation (NI) methods. AFM in the contact mode of lateral forces revealed the presence of different contrast phases on the surface of synthesized films which depends on the chemical structure of monomers used. Single-walled carbon nanotubes (SWCNTs), carbon nanofibers, graphene, tungsten disulfide and tungsten diselenide were introduced into coPUI matrices. Dependencies of microhardness and modulus of elasticity on the depth of indentation have been obtained. It was found that for each synthesized coPUI, there is only one type of carbon nanomaterials that exerts the greatest influence on their characteristics. The improvement of mechanical properties is found to mainly depend on the nature of the polymer matrix and filler. Our results showed that effective methods for improving of tribological characteristics can be either modification by SWCNTs (up to 1 wt.%) or heating at 30°C. Synthesized coPUI films and nanocomposites are very promising materials and can be used as thermoplastic elastomers for tribological applications, and their physical-mechanical properties can be controlled both by temperature and by mechanical action

Novel Semicrystalline Thermoplastic R-BAPB Type Polyimide Matrix Reinforced By Graphite Nanoplatelets and Carbon Nanoparticles

A new semicrystalline polyimide, based on 1. 3-bis-(3,3\u27,4,4\u27-dicarboxyphenoxy) benzene (R) and 4,4\u27-bis(4-aminophenoxy)biphenyl (BAPB), was modified by exfoliated graphite nanoplatelets of different shape, sizes and structure. This R-BAPB type polyimide, with a molecular weight Mw = 30000 g/mol has a low melting temperature of 320 degrees C and a melt zero shear viscosity of about 1000 Pa s at 340 degrees C, making it possible to mix it with particulates using classical melt-blending technology. By using calorimetric and rheological measurements, this study reports a dramatic crystal nucleating effect of the polyimide caused by the special nanographite platelets. In addition, the study shows that classical melt blending of R-BAPB type PI with exfoliated graphite nanoplatelets can be used to prepare useful polyimide nanocomposites with the added benefit of possibly accelerating the crystallization process of the polyimide matrix. Further, it was observed that the time of crystallization at 300 degrees C for the nanocomposites filled with 5 wt% nanographite platelets was about 10 5 minutes, a value corresponding to one-half that of the unfilled R-BAPB type PI matrix

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

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

Effect of Domain Structure of Segmented Poly(urethane-imide) Membranes with Polycaprolactone Soft Blocks on Dehydration of <i>n</i>-Propanol via Pervaporation

Segmented poly(urethane-imide)s (PUIs) were synthesized by polyaddition reaction and applied for preparation of membranes. Tolylene-2,4-diisocyanate, pyromellitic dianhydride, and m-phenylenediamine for chain extension were used to form hard aromatic blocks. Polycaprolactone diols with molecular weights equal to 530 and 2000 g mol&#8722;1 were chosen as soft segments. The effect of the length of soft segments on the structure, morphology, and transport properties of segmented poly(urethane-imide) membranes were studied using atomic force microscopy, small-angle and wide-angle X-ray scattering, and pervaporation experiments. It was found that a copolymer with a shorter soft segment (530 g mol&#8722;1) consists of soft domains in a hard matrix, while the introduction of polycaprolactone blocks with higher molecular weight (2000 g mol&#8722;1) leads to the formation of hard domains in a soft matrix. Additionally, the introduction of hard segments prevents crystallization of polycaprolactone. Transport properties of membranes based on segmented PUIs containing soft segments of different length were tested for pervaporation of a model mixture of propanol/water with 20 wt % H2O content. It was found that a membrane based on segmented PUIs containing longer soft segments demonstrates higher flux (8.8 kg &#956;m m&#8722;2 h&#8722;1) and selectivity (179) toward water in comparison with results for pure polycaprolactone reported in literature. The membrane based on segmented PUIs with 530 g mol&#8722;1 soft segment has a lower flux (5.1 kg &#956;m m&#8722;2 h&#8722;1) and higher selectivity (437)

MODIFICATION OF THE THERMOPLASTIC POLYHETEROARYLENES WITH ALIPHATIC POLYETHERS AND POLYESTERS: SYNTHESIS AND DYNAMIC MECHANICAL PROPERTIES

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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