Search Results (11)

Morphology, macro-, and micromechanical properties of novel poly(urethane-urea)/silica nanocomposites were analyzed by electron microscopy, dynamic mechanical thermal analysis, and microindentation. The studied nanocomposites were based on a poly(urethane-urea) (PUU) matrix filled by nanosilica, and were prepared from waterborne dispersions of PUU (latex) and SiO₂. The loading of nano-SiO₂ was varied between 0 (neat matrix) and 40 wt% in the dry nanocomposite. The prepared materials were all formally in the rubbery state at room temperature, but they displayed complex elastoviscoplastic behavior, spanning from stiffer elastomeric type to semi-glassy. Because of the employed rigid and highly uniform spherical nanofiller, the materials are of great interest for model microindentation studies. Additionally, because of the polycarbonate-type elastic chains of the PUU matrix, hydrogen bonding in the studied nanocomposites was expected to be rich and diverse, ranging from very strong to weak. In micro- and macromechanical tests, all the elasticity-related properties correlated very strongly. The relations among the properties that related to energy dissipation were complex, and were highly affected by the existence of hydrogen bonding of broadly varied strength, by the distribution patterns of the fine nanofiller, as well as by the eventual locally endured larger deformations during the tests, and the tendency of the materials to cold flow. Full article

Hydrogen bonding in polyurethane (PU) is imposed by molecular parameters. In this study, the effect of structural isomerism of certain monomers on hydrogen bonding of waterborne polyurethane (WBPU) was studied theoretically and experimentally. Two dihydroxybenzene (DHB)-based structural isomers such as catechol (CC) and hydroquinone (HQ), with different OH positions on the inner benzene core, had been used. Two series of WBPU dispersions were prepared using CC and HQ with defined contents. The binding energies between the catechol (CC)/hydroquinone (HQ) (respective OH group) and urethane/urea were calculated theoretically. By using a density functional theory (DFT) method, it was found that the largest binding energy between the urea and CC was higher than that of urea and HQ. The FT-IR analysis of synthesized polymer was also carried out to compare the results with the theoretical values. The CC-based polymers showed a stronger hydrogen bond both theoretically and experimentally than those for HQ-based polymers. The higher level of hydrogen bond was reflected in their properties of CC-based polymers. The adhesive strength, thermal stability, and hydrophobicity were higher for CC-based materials than those for HQ-based materials. The adhesive strength was increased 25% with the addition of 2.0 wt% CC content. This adhesive strength slightly deviated at a moderately high temperature of 80 °C. Full article

Waterborne polyurethane-urea dispersions (WPUD), which are based on fully biobased amorphous polyester polyol and isophorone diisocyanate (IPDI), have been successfully synthesized obtaining a finishing agent that provides textiles with an enhanced hydrophobicity and water column. Grafting of trans-cyclohexanediol isobutyl POSS (POSS-OH) to the biobased polymer backbone has also been investigated for the first time and its properties compared to a standard chain extender, 1,3-propanediol (PDO). The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Mechanical properties have been studied by tensile stress–strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, storage aging tests, and accelerated aging tests by analytical centrifuge (LUM). Subsequently, selected fabrics have been face-coated by the WPUD using the knife coating method and their properties have been assessed by measuring the water contact angle (WCA), oil contact angle (OCA), water column, fabric stiffness, air permeability, and water vapor resistance (breathability). Finally, the surface morphology and elemental composition of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. All of the synthesized polyurethane-ureas provided the coated substrates with a remarkable hydrophobicity and water column, resulting in a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. Grafting POSS-OH to the polymeric backbone has led to textile coatings with enhanced hydrophobicity, maintaining thermal, mechanical, and water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles. Full article

Small amounts—0.04 wt.%—graphene oxide derivatives with different surface chemistry (graphene oxide—GO-, amine-functionalized GO—A-GO-, reduced GO—r-GO) were added during prepolymer formation in the synthesis of waterborne poly(urethane urea) dispersions (PUDs). Covalent interactions between the surface groups on the graphene oxide derivatives and the end NCO groups of the prepolymer were created, these interactions differently altered the degree of micro-phase separation of the PUDs and their structure–properties relationships. The amine functional groups on the A-GO surface reacted preferentially with the prepolymer, producing new urea hard domains and higher percentage of soft segments than in the PUD without GO derivative. All GO derivatives were well dispersed into the PU matrix. The PUD without GO derivative showed the most noticeable shear thinning and the addition of the GO derivative reduced the extent of shear thinning differently depending on its functional chemistry. The free urethane groups were dominant in all PUs and the addition of the GO derivative increased the percentage of the associated by hydrogen bond urethane groups. As a consequence, the addition of GO derivative caused a lower degree of micro-phase separation. All PUs containing GO derivatives exhibited an additional thermal decomposition at 190–206 °C which was ascribed to the GO derivative-poly(urethane urea) interactions, the lowest temperature corresponded to PU+A-GO. The PUs exhibited two structural relaxations, their temperatures decreased by adding the GO derivative, and the values of the maximum of tan delta in PU+r-GO and PU+A-GO were significantly higher than in the rest. The addition of the GO derivative increased the elongation-at-break, imparted some toughening, and increased the adhesion of the PUD. The highest T-peel strength values corresponded to the joints made with PUD+GO and PUD+r-GO, and a rupture of the substrate was obtained. Full article

Waterborne polyurethane-urea dispersions (WPUD), which are based on 100% bio-based semi-crystalline polyester polyol and isophorone diisocyanate, have been successfully synthesized and doped with single-walled carbon nanotubes (SWCNT) to obtain a finishing agent that provides textiles with multifunctional properties. The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). Mechanical properties have been studied by tensile stress–strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, and accelerated aging tests (analytical centrifugation). Subsequently, selected fabrics have been face-coated by the WPUD using knife coating method and their properties have been assessed by measuring water contact angle (WCA), water column, fabric stiffness, and air permeability. The electrical conductivity of textiles coated with SWCNT-doped WPUD has been evaluated by EN 1149 standard. Finally, the surface morphologies of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM). All of the synthesized polyurethane-ureas provide the coated substrates with remarkable water-repellency and water column, being therefore a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. The additivation of the polymeric matrices with SWCNT has led to textile coatings with excellent electrical conductivity, maintaining water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles. Full article

Polyurethanes and polyurethane-ureas, particularly their water-based dispersions, have gained relevance as an extremely versatile area based on environmentally friendly approaches. The evolution of their synthesis methods, and the nature of the reactants (or compounds involved in the process) towards increasingly sustainable pathways, has positioned these dispersions as a relevant and essential product for diverse application frameworks. Therefore, in this work, it is intended to show the progress in the field of polyurethane and polyurethane-urea dispersions over decades, since their initial synthesis approaches. Thus, the review covers from the basic concepts of polyurethane chemistry to the evolution of the dispersion’s preparation strategies. Moreover, an analysis of the recent trends of using renewable reactants and enhanced green strategies, including the current legislation, directed to limit the toxicity and potentiate the sustainability of dispersions, is described. The review also highlights the strengths of the dispersions added with diverse renewable additives, namely, cellulose, starch or chitosan, providing some noteworthy results. Similarly, dispersion’s potential to be processed by diverse methods is shown, evidencing, with different examples, their suitability in a variety of scenarios, outstanding their versatility even for high requirement applications. Full article

A series of waterborne polycarbonate-based poly(urethane-urea) nanocomposite films were prepared and characterized. An isocyanate excess of 30 mol% with respect to the hydroxyl groups was used in the procedure, omitting the chain-extension step of the acetone process in the dispersion preparation. The individual steps of the synthesis of the poly(urethane-urea) matrix were followed by nuclear magnetic resonance (NMR) spectroscopy. The nanofillers (1 wt% in the final nanocomposite) differed in nature and shape. Starch, graphene oxide and nanocellulose were used as representatives of organic nanofillers, while halloysite, montmorillonite, nanosilica and hydroxyapatite were used as representatives of inorganic nanofillers. Moreover, the fillers differed in their shape and average particle size. The films were characterized by a set of methods to obtain the tensile, thermal and surface properties of the nanocomposites as well as the internal arrangement of the nanoparticles in the nanocomposite film. The degradation process was evaluated at 37 °C in a H₂O₂ + CoCl₂ solution. Full article

In this study, 0.04 wt % graphene oxide (GO) was added in different stages (before and after prepolymer formation, and during water addition) of the synthesis of waterborne polyurethane-urea dispersions (PUDs) prepared by using the acetone method. The structural, thermal, mechanical, viscoelastic, surface and adhesion properties of the polyurethane-ureas (PUUs) containing 0.04 wt % GO were studied. The addition of GO before and after prepolymer formation produced covalent bonds between the GO sheets and the NCO groups of the isocyanate, whereas the GO sheets were trapped between the polyurethane chains when added during water addition step. As a consequence, depending on the stage of the PUD synthesis in which GO was added, the degree of micro-phase separation between the hard and soft segments changed differently. The addition of GO before prepolymer formation changed more efficiently the polyurethane-urea structure, i.e., the covalently bonded GO sheets disturbed the interactions between the hard segments causing lower percentage of free urethane groups, higher crystallinity, lower storage modulus, higher yield stress and T-peel strength. The interactions between the GO sheets and the polymeric chains have been evidenced by plate-plate rheology, thermal gravimetric analysis and spectroscopy. On the other hand, physical interactions between GO and the polyurethane-urea chains were produced when GO was added in water during the synthesis, i.e., GO was acting as a nanofiller, which justified the improved mechanical properties and high lap-shear strength, but poor T-peel strength. Full article

New waterborne polyurethane-urea dispersions with adequate adhesion and cohesion properties have been synthesized by reacting isophorone diisocyanate, copolymer of ether and carbonate diol polyol and three amino-alcohols with different number of OH groups chain extenders using the prepolymer method. The waterborne polyurethane-urea dispersions were characterized by pH, particle-size distribution, and viscosity, and the polyurethane-urea films were characterized by attenuated total reflectance infrared (ATR-IR) spectroscopy, differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and plate-plate rheology (temperature and frequency sweeps). Polyurethane-urea pressure-sensitive adhesives (PUU PSAs) were prepared by placing the waterborne polyurethane dispersions on polyethylene terephthalate (PET) films and they were characterized at 25 °C by creep test, tack and 180° peel test. The waterborne polyurethane-urea dispersions showed mean particle sizes between 51 and 78 nm and viscosities in the range of 58–133 mPa·s. The polyurethane-urea films showed glass transition temperatures (T_gs) lower than −64 °C, and they showed a cross of the storage and loss moduli between −8 and 68 °C depending on the number of OH groups in the amino-alcohol chain extender. Different types of PUU PSAs (removable, high shear) were obtained by changing the number of OH groups in the amino-alcohol chain extender. The tack at 25 °C of the PUU PSAs varied between 488 and 1807 kPa and the 180° peel strength values ranged between 0.4 and 6.4 N/cm, and their holding times were between 2 min and 5 days. The new PUU PSAs made with amino-alcohol chain extender seemed very promising for designing environmentally friendly waterborne PSAs with high tack and improved cohesion and adhesion property. Full article

This research work was focused on the incorporation of TiO₂ nanoparticles into synthesized solvent-free waterborne poly(urethane-urea) (WPUU) based on hydrophilic poly(ethylene oxide) (PU0) in order to improve both the mechanical properties and self-healing effectiveness of a polymer matrix. The incorporation of TiO₂ nanoparticles resulted in a successful enhancement of the mechanical properties of nanocomposite films when compared to PU0. Simultaneously, the obtained nanocomposite films did not only maintain the self-healing ability of the PU0 film, measured by means of mechanical properties after successive cutting/recovery cycles, but they also showed a higher self-healing efficiency than the PU0 film. Moreover, the well-dispersed TiO₂ nanoparticles, visualized by atomic force microscopy (AFM), kept their conductive properties when embedded in the PU0 matrix, as was confirmed by electrostatic force microscopy (EFM). This research work described a simple and industrially appealing way to control the dispersion of commercially available TiO₂ nanoparticles in waterborne poly(urethane-urea) for the designing of inorganic/organic hybrid nanocomposites with enhanced mechanical properties and self-healing efficiency, in which TiO₂ nanoparticles preserved their conductive properties within the polymer matrix. Full article

Regenerated cellulose nanoparticles (RCNs) reinforced waterborne polyurethanes (WPU) were developed to improve mechanical properties as well as biodegradability by using a facile, eco-friendly approach, and introducing much stronger chemical bonding than common physical bonding between RCNs and WPU. Firstly, RCNs which have an effect on improving the solubility and stability of a solution, thereby resulting in lower crystallinity, were fabricated by using a NaOH/urea solution. In addition, the stronger chemical bond between RCNs and WPU was here introduced by regarding at which stage in particular added RCNs worked best on strengthening their bond in the process of WPU synthesis. The chemical structure, mechanical, particle size and distribution, viscosity, and thermal properties of the resultant RCNs/WPU nanocomposites were investigated by Fourier transform infrared analysis (FTIR), Zeta-potential analysis, viscometer, thermogravimetric analysis (TGA), Instron, and dynamic mechanical analysis (DMA). The results of all characterizations indicated that the RCNs/WPU-DMF associated with the addition of RCNs in DMF-dispersed step resulted in more effectively crosslinked between WPU and nano-fillers of nanocellulose particles in the dispersion than Acetone and Water-dispersed steps, thereby attributing to novel interactions formed between RCNs and WPU. Full article