Adhesion Mechanisms of Polyurethanes to Glass Surfaces. III. Investigation of Possible Physico-Chemical Interactions at the Interphase

Surface free energies of polyurethanes made from toluene diisocyanate and 1, 4 butanediol-based hard segments and caprolactone polyol-based soft segments were calculated using additive functions. Good agreement was found between the calculated values based on additive functions and the calculated values based on contact angle measurements. The phase-separated polyurethanes were found to have a higher polar surface free energy component (γ^P). This was linked to the preferential segregation of butanediol/butanediol-derived moieties to the polyurethane surfaces due to phase separation. The adhesion values of these polyurethanes to soda-lime glass were correlated with their respective γ^P values and a linear relationship was found. It was also shown that the adhesion values of the low γ^P polyurethanes improved substantially when the glass surfaces were coated with a thin layer of butanediol prior to the bonding. The modulus of the interphase region rich in butanediol was evaluated. Although a modulus increase was found at the interface, this increase was found to play a secondary role in the adhesion. The chemical interactions at the polyurethane/glass interphase were investigated by pre-treating the glass surfaces with methyl-trimethoxysilane and trimethylchlorosilane prior to adhesion testing. The adhesion data showed no significant difference between the uncoated and the silane-treated glass substrates. Based on this experimental evidence, the possibility of any covalent or ionic bonding at the polyurethane/glass interphase was assumed negligible. It was determined that the mechanism of adhesion between the polyurethanes and the glass surface could be through the formation of an interphase region in which hydrogen bonding between the butanediol-rich interphase region and the hydroxylated glass surface plays a key role.     

Electrospinning of polyurethane fibers

A segmented polyurethaneurea based on poly(tetramethylene oxide)glycol, a cycloaliphatic diisocyanate and an unsymmetrical diamine were prepared. Urea content of the copolymer was 35 wt%. Electrospinning behavior of this elastomeric polyurethaneurea copolymer in solution was studied. The effects of electrical field, temperature, conductivity and viscosity of the solution on the electrospinning process and morphology and property of the fibers obtained were investigated. Results of observations made by optical microscope, atomic force microscope and scanning electron microscope were interpreted and compared with literature data available on the electrospinning behavior of other polymeric systems.     

改性偶氮二甲酰胺/水复合发泡在硬质聚氨酯发泡中的应用研究

目的 通过偶氮二甲酰胺(AC)热分解反应释放出发泡用气体,用改性偶氮二甲酰胺/水复合发泡制备无卤素硬质聚氨酯泡沫(RPUF)。探讨改性偶氮二甲酰胺在聚氨酯发泡中的可行性。方法 通过改变体系中改性偶氮二甲酰胺的用量,探讨改性偶氮二甲酰胺对聚醚发泡体系黏度、聚氨酯泡沫力学性能和导热系数的影响。结果 发泡剂的加入能显著降低聚醚体系的黏度,提高发泡物料的流动性,随着改性AC用量的增加,体系黏度逐渐增加,当改性AC的添加量为0.3 g时,体系黏度最低为2 080 mPa.s。当改性AC用量为0.75 g时,聚氨酯泡沫的表观密度为78.65 kg/m³,压缩强度为539.35 kPa,改性AC的加入使得聚氨酯泡沫的导热系数增高,导热系数为0.023 51 W/mK。结论 改性AC的加入能显著提高硬质聚氨酯泡沫的压缩强度,相比纯水发泡,二者复合发泡性能更优异,可以作为无卤素发泡剂应用于聚氨酯发泡。     

Effect of soft-hard segment structure on vapor responsiveness of polyurethane conducting composite thin films loaded with multi-walled carbon nanotubes

A series of multi-walled carbon nanotubes/polyurethane (MWNTs/PU) composite conducting dispersoids were prepared via an in situ coupling reaction among linear hydroxyl-terminated polymer diols, 1,6-hexamethylene diisocyanate (HDI) and various chain extenders. The composite conducting thin films were formed by spin-coating and depositing the dispersoids onto comb-like electrode substrates. The resulting structure and the dispersion quality of MWNTs in the dispersoids were examined by means of FTIR, XRD, TEM, SEM and UV-vis analyses. The response of the as-prepared films toward some volatile organic solvent vapors such as benzene, anhydrous ether, acetone and chloroform was evaluated. The experimental results indicated that the composite conducting films constructed by hydroxyl-terminated poly(butadiene-co-acrylonitrile), trimethylolpropane, and MWNTs-OH bear better vapor responsiveness. The dispersion behavior of MWNTs in the dispersoids, types of MWNTs and soft-hard segmental compositions are believed to be closely related with the sensing properties of the films. In particular, the chemical linkage of MWNT-OH with HDI in the PU matrix is expected to improve the dispersivity and further to enhance the sensing properties of the composite sensors. The vapor sensing properties well reveal that these materials have a possibility as a candidate of volatile organic solvent vapor sensors.     

The interfacial interaction between isocyanate and stainless steel

The interfacial interactions between methylene diphenyl di-isocyanate (MDI) and polymeric MDI (PMDI) with 316L stainless steel have been studied in order to understand the adhesion properties of polyurethane based adhesives (containing free isocyanate groups) on metal surfaces. A thin (<5 nm) layer of MDI and PMDI was deposited on the surface of clean 316L stainless steel and then analysed by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF-SIMS). By using density functional theory (DFT) methods for the interpretation of XPS data, the presence of specific interactions between the adsorbate and the substrate was established. The reaction between isocyanate and metal hydroxyl groups with the formation of urethane-like bonding with the metal was observed. The formation of hydrogen bonds between the isocyanate nitrogen and the hydroxyl groups and the formation of a nitrogen-metal double bond, as a consequence of the cycloaddition reaction between isocyanate and metal oxide, are also proposed.     

Fixation of ionic liquids into polyether-based polyurethane films to maintain long-term antistatic properties

Ionic liquids (ILs) were fixed into polyether-based polyurethane (PU) films for sustainable antistatic properties. Preliminarily, ILs were screened in terms of efficiency of antistatic effect. Surface resistivity (ρ_s) for IL-doped PU films changed depending the anion species, and the smallest ρ_s was found for the PU films containing bis(trifluoromethanesulfonyl)imide ([Tf₂N])-type ILs. Then, [Tf₂N]-type ILs composed of ammonium cations having hydroxyl groups were fixed into the PUs through urethane bonds. The fixation of 1000 ppm of the ILs reduced the ρ_s of the PU films from 2.1 × 10¹² to 2.1 × 10⁹ Ω sq⁻¹. These IL-fixed PU films were revealed to possess high washing durability confirmed by negligible change of ρ_s before and after ultra-sonication treatment in methanol.     

Polyurethane/graphite nano-platelet composites for thermal energy storage

In this work new polyurethane-based phase change materials containing segments of poly(ethylene glycol) with average molar mass of 8000 g/mol with and without chain extender and modified with graphite nano-platelets have been fabricated and characterized. Structure, morphology and phase behaviour of these solid-solid phase change materials were investigated, as well as the thermal stability and conductivity. The heat of phase transition was in the range of 118.0–164.5 J/g for polyurethane without chain extender and 128.0–148.5 J/g for polyurethane with chain extender. The highest heat of phase transition and crystallinity were found for system modified with 0.3% of graphite nano-platelets in polyurethane without chain extender. Modulated differential scanning calorimetry results showed some changes in the phase transition behaviour and the crystallinity of the polyurethane matrix due to graphite nano-platelets confinement effect. Enhancements in the thermal stability in polyurethane modified with graphite nano-platelets, attributed to the barrier effect, were found based on thermogravimetric analysis data. The thermal conductivity increased with an increase of graphite nano-platelets content for both polyurethane systems, with and without chain extender, which is important for modern thermal energy storage applications.     

Natural Palm Olein Polyol as a Replacement for Polyether Polyols in Viscoelastic Polyurethane Foam

The impact of replacing three polyether polyols with different levels of a single palm olein‐based natural oil polyol (NOP) was systematically correlated with the changes in foaming reactivity, cell structure, physico‐mechanical properties, and morphology of viscoelastic (VE) foams. The data show that replacing the polyether polyols with the NOP slightly increased the rate of the foaming reactivity. Increasing the NOP content resulted in increased cell size and cells remained fully open. Increased NOP content contributed to higher load bearing properties of VE foam, which can be attributed to higher functionality of NOP compared to polyether polyols. Addition of the NOP slightly increased the resilience of the foams, however, the hysteresis which is the measure of energy absorption remained mostly unaffected. Age properties, characterized by dry and humid compression sets, were mostly unaffected by the replacement of the polyether polyol with the NOP. The addition of NOP did not impact the morphology of the VE foam polymer matrix, which appears to retain a low degree of hard and soft segment domain separation. Overall, the results demonstrate a feasibility that the NOP can be used to partially replace the polyether polyols in VE polyurethane foams without significant impact on the functional performance.     

Ageing behavior of acrylic polyurethane varnish coating in artificial weathering environments

Polyurethane-based coatings reinforced by ZnO nanoparticles (about 27 nm) were prepared via solution blending. The ZnO/PU films and coats were fabricated by a simple method of solution casting and evaporation. The mechanical properties of the films were investigated by a universal material test, and the abrasion resistance of the prepared coats was evaluated by a pencil-abrasion-resistance tester. It was found that significant improvement of the PU films in Young’s modulus and tensile strength was achieved by incorporating ZnO nanoparticles up to 2.0 wt%, and that the abrasion resistance of the PU coats was greatly enhanced due to the addition of ZnO nanoparticles. Moreover, the antibacterial property test was carried out via the agar dilution method and the result indicated that PU films doped with ZnO nanoparticles showed excellent antibacterial activity, especially for Escherichia coli.     

Use of hydroxytelechelic cis-1,4-polyisoprene (HTPI) in the synthesis of polyurethanes (PUs). Part 1. Influence of molecular weight and chemical modification of HTPI on the mechanical and thermal properties of PUs

New telechelic cis-1,4-polyisoprene oligomers bearing an hydroxyl group at the end of the polyisoprene backbone and possessing controlled molecular weights were used as soft segments in the elaboration of polyurethane elastomers. Besides, the well defined hydroxytelechelic cis-1,4-polyisoprene (HTPI) structure obtained through a controlled methodology, was chemically modified leading to hydrogenated and epoxidized oligomers based polyurethanes. The influence of the structural changes of these precursors on the polyurethanes properties have been studied. Thus, mechanical parameters as well as glass transition and mechanical transition temperature measurements indicated an increase in PUs hardness when the length of soft segment decreases and when the degree of epoxidized and hydrogenated isoprenic moieties increases. Moreover, based on thermogravimetric analysis (TGA), a linear relationship was established between the weight loss in the urethane stage degradation and the amount of hard segments in the PUs. Otherwise, the hydrogenated soft segments were found more thermally stable than the epoxidized and the non modified ones. By comparison with similar investigations developed from commercial oligodienes (PBHT R20 LM^® and EPOL^®), this study mainly showed that the PUs based on hydrogenated hydroxytelechelic cis-1,4-polyisoprenes were more thermally stable and softer than the EPOL^® based analogues.