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

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)

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

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