Preparation and properties of starch thermoplastics modified with waterborne polyurethane from renewable resources

A waterborne polyurethane (PU) aqueous dispersion was synthesized from castor oil, and blended with thermoplastic starch (TPS) to obtain a novel biodegradable plastic with improved physical properties. The effect of PU content on the morphology, miscibility and physical properties of the resulting blends was well investigated by scanning electron microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis and measurements of mechanical properties and water sensitivity. The research results show that the blends exhibit a higher miscibility when PU content is lower than 15 wt% due to the hydrogen bonding interaction between urethane groups and hydroxyl groups on starch, whereas obviously phase separation occurs in the blends with more than 15 wt% PU. Incorporating PU of 4-20 wt% in TPS results in the blends with improved Young's modulus (40-75 MPa), tensile strength (3.4-5.1 MPa), elongation at break (116-176%). Further, PU also plays an important role in improving the surface- and bulk-hydrophobicity and water resistance of the resulting blends.     

Effects of solid substrate on structure and properties of casting waterborne polyurethane/carboxymethylchitin films

We prepared two series of semiinterpenetrating polymer network (semi-IPN) films from cross-linked waterborne polyurethane (WPU) and carboxymethylchitin (CMCH) in the aqueous solution on the glass and Teflon as the hydrophilic and hydrophobic substrates, respectively, by casting method. The chemical compositions, structure and morphologies of the films were examined by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM). The miscibility, thermal stability and mechanical properties of the films were investigated by density measurement, dynamic mechanical analysis (DMA), ultraviolet (UV) spectroscopy, thermogravimetric analysis (TGA), tensile testing and solvent swelling testing. The results revealed that the semi-IPN films exhibited good miscibility when CMCH content was lower than 35 and 65 wt% for the films prepared on the glass and Teflon, respectively, resulting in higher light transmittance, thermal stability and tensile strength than the WPU film. Interestingly, the films prepared with the Teflon as the substrate possessed better miscibility and higher storage modulus, thermal stability, tensile strength and solvent-resistance than that with the glass as the substrate over the entire composition range studied here. This difference can be attributed that a strong intermolecular interaction occurred between WPU and CMCH to form a dense architecture, owing to that two kinds of macromolecules all were repulsed from the Teflon surface and forced to concentrate into inner surface. It has been confirmed that the hydrophility and hydrophobility of the solid substrate significantly influenced the structures and properties of the casting films, and using Teflon solid substrate can more effectively improve the miscibility and properties of the semi-IPN materials with hydrophilic character than glass one. We proposed a model describing the formation of WPU/CMCH semi-IPN films cast on the hydrophilic and hydrophobic substrates to illustrate the different structures of two types of films.     

Miscibility, free volume behavior and properties of blends from cellulose acetate and castor oil-based polyurethane

A series of blend films from cellulose acetate (CA) and castor oil-based polyurethane (PU) were prepared. Morphology, miscibility, free volume behavior and properties of such blend films were investigated by wide-angle X-ray diffraction (WXRD), infrared, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), positron annihilation lifetime spectroscopy (PALS), thermogravimetric analysis and tensile test. The results indicated that lager free volume cavities did not form at the interface of two polymers although a certain degree of phase separation was found by the studies of SEM and DSC. Strong intermolecular hydrogen bonding interactions at the interface, which was proved by Fourier transform infrared spectroscopy, favors even better molecular packing, that is, PU dispersed in CA continuous phase to form fine microphase separation domain in the CA-rich blends. Due to such special interactions in the fine microphase separation domain structure, optimized properties of tensile strength, breaking elongation and cold-resistivity were obtained in the blend film with 75 wt% CA. The toughness of all the blend films was significantly higher than that of the film CA, owing to the plasticizing of PU elastomer in the blends.     

Studies on characterization and cryogenic mechanical properties of polyimide-layered silicate nanocomposite films

Polyimide/layered silicate nanocomposites were prepared via in situ polymerization process from PMDA-ODA and organo-MMT in a solution of N,N-dimethylacetamide. XRD, FTIR, UV-vis analyses showed that at the content of 1 wt% MMT, MMT were well intercalated, exfoliated and dispersed in polyimide matrix. As the MMT content is more than 3 wt%, MMT agglomerates became severe as shown by the transparency and transmittance of the hybrid films. The cryogenic mechanical properties of the films at 77 K were studied and compared with those at room temperature. The cryogenic tensile strength showed the highest value at 1 wt% MMT content, and its strength, modulus and elongation at break were simultaneously increased than the pure PI film. The cryogenic elastic modulus exhibited an increasing trend until the MMT content reached 10 wt%. The cryogenic failure strain of hybrid films with 1-3 wt% MMT contents was greater than 10%, showing good ductility at 77 K. The tensile strength and modulus of the hybrid films at 77 K were generally higher than those at room temperature except at 20 wt% MMT for the strength.     

Effects of AN-contents and shear flow on the miscibility of PC/SAN blends

The miscibility of polycarbonate (PC) with styrene-co-acrylonitrile random copolymer (SAN) has been systematically investigated as functions of acrylonitrile content and shear flow. Various AN-contents ranged from 11 to 74 wt% and different simple shear flow values up to 90 s⁻¹ have been used to explore the effect of both material and proceeding parameters on the miscibility of PC and SAN blends. The finest phase dispersion of the SAN particles was observed at AN=25 wt% for PC/SAN=70/30 blends under the same processing condition using scanning electron microscope (SEM). The obtained morphologies indicated that PC and SAN could form a partial miscibility blend and the maximum miscibility occurred at AN=25 wt%. This observation was supported by considering the shifts in the glass processes of the two rich phases of the blend using the dynamical mechanical analysis (DMA) measurements. The optimum interaction of the two components at AN=25 wt% calculated from ellipsometric technique was found to be the only responsible parameter for the high miscibility of the blend. The viscoelastic properties of the pure polymer components were found to play a minor role in the obtained morphologies. The effect of simple shear flow on the morphology of PC/SAN-25=70/30 blend has been also investigated using a special shear apparatus of parallel plate geometry. It has been found that the dispersed phase of SAN was elongated and broken-up in the direction of flow with weaker contrast at high shear rates. The shear rate was found to enhance the miscibility of SAN (dispersed phase) in the PC matrix to a great extent as seen in the weak contrast of the two phases observed by transmission electron microscope (TEM).     

Effects of NCO/OH molar ratio on miscibility and properties of semiinterpenetrating polymer networks from polyurethane and benzyl konjac glucomannan

Semi‐interpenetrating polymer network (semi‐IPN) films with different NCO/OH molar ratios of the urethane prepolymer, coded as UB, were prepared from polyurethane (PU) and benzyl konjac glucomannan (B‐KGM) by a casting method. The effect of the NCO/OH molar ratio of the urethane prepolymer on the miscibility and properties of the UB films was investigated using Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, thermogravimetric analysis, and swelling and tensile tests. The results indicated that, with an increase of the NCO/OH ratio, the crosslink density of the UB films increased, resulting in improved miscibility between PU and B‐KGM and a relatively high light transmittance of the UB films. However, the thermal stability of the UB films decreased with increase of the NCO/OH ratio of the urethane prepolymer, due to the depolymerization of the urethane bonds of the PU networks. When the NCO/OH ratio increased from 2 to 4, the tensile strength of the UB films increased from 15 to 27 MPa, while the breaking elongation decreased from 72 to 16%, resulting from the chemical and physical crosslinks, namely, the enhancement of the covalent bonds and hydrogen‐bonding networks. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1304–1310, 2003     

Toughening of poly(butylene terephthalate) with epoxy-functionalized acrylonitrile-butadiene-styrene

Glycidyl methacrylate (GMA) functionalized acrylonitrile-butadiene-styrene (ABS) copolymers have been prepared via an emulsion polymerization process. These functionalized ABS copolymers (ABS-g-GMA) were blended with poly(butylene terephthalate) (PBT). DMA result showed PBT was partially miscible with ABS and ABS-g-GMA, and DSC test further identified the introduction of GMA improved miscibility between PBT and ABS. Scanning electron microscopy (SEM) displayed a very good dispersion of ABS-g-GMA particles in the PBT matrix compared with the PBT/ABS blend when the content of GMA in PBT/ABS-g-GMA blends was relatively low (<8 wt% in ABS-g-GMA). The improvement of the disperse phase morphology was due to interfacial reactions between PBT chains end and epoxy groups of GMA, resulting in the formation of PBT-co-ABS copolymer. However, a coarse, non-spherical phase morphology was obtained when the disperse phase contained a high GMA content (≥8 wt%) because of cross-linking reaction between the functional groups of PBT and GMA. Rheological measurements further identified the reactions between PBT and GMA. Mechanical tests showed the presence of only a small amount of GMA (1 wt%) within the disperse phase was sufficient to induce a pronounced improvement of the impact and tensile properties of PBT blends. SEM results showed shear yielding of PBT matrix and cavitation of rubber particles were the major toughening mechanisms.     

Thermotropic liquid crystalline polymer (Rodrun LC5000)/polypropylene in situ composite films: rheology, morphology, molecular orientation and tensile properties

In situ composite films were prepared by a two-step method. First, polypropylene and thermotropic liquid crystalline polymer (TLCP), Rodrun LC5000 (80 mol% p-hydroxy benzoic acid (HBA)/20 mol% polyethylene terephthalate (PET)), were melt blended in a twin-screw extruder and then fabricated by extrusion through a mini-extruder as cast film. Rheological behavior of the blends, morphology of the extruded strands and films, and tensile properties of the in situ composite films were investigated. Rheological behavior of the blends at 295 °C studied using a plate-and-plate rheometer revealed a substantial reduction of the complex viscosity with increasing TLCP content, and all specimens exhibited shear thinning behavior. Over the angular frequency range of 0.6-200 rad/s, the viscosity ratio (dispersed phase to matrix phase) was found to be very low, in the range of 0.03-0.07. Morphologies of the fracture surfaces of the blend extrudates and the film surfaces etched in permanganic solution were investigated by scanning electron microscope (SEM). The TLCP droplets in the extruded strands were seen with a progressive deformation into fibrillar structure when TLCP content was increased up to 30 wt%. In the extruded films, TLCP fibrils with increasing aspect ratio (length to width) were observed with increasing TLCP concentration. Orientation functions of each component were determined by X-ray diffraction using a novel separation technique. It was observed that the Young's modulus in machine direction of the extruded film was greatly improved with increasing TLCP loading, due to the increase in fiber aspect ratio and also molecular orientation.     

Semi-interpenetrating polymer networks from castor oil-based polyurethane and nitrokonjac glucomannan

New semi-interpenetrating polymer networks (semi-IPNs) coded as PUNK were successfully synthesized from castor oil-based polyurethane (PU) prepolymer and 10–40 wt % nitrokonjac glucomannan (NKGM) containing a degree of substitution of 2.4 and a weight-average molecular weight of 4.75 × 10⁴. The semi-IPN sheets that were 100 μm thick were cured more speedily than PU, with curing times of 5 h for PUNK and 16 h for PU at 50–70°C. The structure and miscibility of the semi-IPN sheets were studied by Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and scanning electron microscopy. The results showed that a strong intermolecular interaction caused by hydrogen bonding between NKGM and PU exists in PUNK, resulting in good miscibility. When the NKGM content of the semi-IPNs sheets was 20 wt %, the tensile strength and light transmittance were obviously higher than that of the PU sheets. The NKGM in the semi-IPN sheets plays an important role not only in accelerating the cure but also in improving the mechanical properties and biodegradability. As a new material prepared from renewable resources, PUNK has potential applications because of its biodegradability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2076–2083, 2001     

A novel castor oil-based polyurethane/layered zirconium phosphonate nanocomposites: preparation,characterization, and properties

A new type of layered zirconium glycine-N,N-dimethylphosphonate (ZGDMP), with the functional groups –COOH, has been prepared and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). Situ polymerization method was employed to prepare castor oil-based polyurethane/layered zirconium phosphonate (PU/ZGDMP-n) nanocomposite films. The structure and morphology of ZGDMP in PU matrix have been characterized by XRD, SEM, TEM, and Fourier transform infrared spectroscopy. The results show that the morphology and properties of PU-based nanocomposites greatly depend on the functional groups –COOH because of the chemical reactions and physical interactions involved. The tensile test shows that the tensile strength and elongation at break for the nanocomposite films increase with the loading of ZGDMP as compared to those of the virgin PU.     

Exploring long-range connectivity of the hard segment phase in model tri-segment oligomeric polyurethanes via lithium chloride

The influence of the extent of hydrogen bonding in mediating the long-range connectivity and percolation of the hard segment phase in model tri-segment oligomeric polyurethanes (PU) was explored by using LiCl as a molecular probe. A 22 wt% hard segment containing model PU plaque based on a mono-functional oligomeric polyether, 80:20 2,4:2,6 isomeric mixture of toluene diisocyanate, and water as a chain extender was employed. Samples cast from 20 wt% solutions in dimethyl acetamide were utilized. The tapping-mode atomic force microscopy (AFM) phase image of the solution cast film sample (soft segment T_g −63 °C) without LiCl exhibited the presence of long interconnected ribbon-like hard domains. The long-range connectivity and percolation of the hard phase that arose during plaque formation gave rise to a brittle rigid solid. A systematic break-up of the hard domains was also observed by AFM when the concentration of LiCl was increased from 0.1 to 1.5 wt%. DSC analysis indicated that the samples were able, however, to maintain a microphase separated morphology even at the highest LiCl concentration utilized in the study. FT-IR data confirmed that LiCl interacts with the hard domains of the model PU samples by disrupting the hydrogen bonding capability of the urea hard segments. A systematic softening of the samples was observed with increasing LiCl content as confirmed by thermomechanical analysis. Thus, this study indicates that hydrogen bonding plays an important role in assisting the hard segments in PU to develop long-range connectivity and percolation of this phase through the soft matrix.     

Effects of ZnO nanoparticles on the mechanical and antibacterial properties of polyurethane coatings

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.     

Double phase separation in preparing polyimide/silica hybrid films by sol-gel method

In this paper, the phase separation process of the polyimide/silica hybrid films made from polyamic acid (PAA) and precursor (TEOS-A) hydrolyzed tetraethoxysilane under acidic condition in N-methyl-2-pyrrolidone (NMP) through sol-gel method was investigated by the scanning electron microscope (SEM). A double phase separation was discovered for the preparation of the hybrid films. With evaporation of the solvent NMP at lower than 100 °C, the component miscibility of TEOS-A and PAA decreases so that the first phase separation took place and a larger particle phase of TEOS-A precursor with size around 2.0 μm was formed. The second phase separation from the matrix phase appeared, as PAA was imidized at elevated temperature, which destroyed the interaction between carboxyl group of PAA and hydroxyl group of TEOS-A, and a nanoscale SiO₂ particle phase formed. The formation mechanism of the double phase separation was explained by the “capture-release” model. According to the model, the second phase separation can be controlled by synthesizing amic acid-imide copolymer with different contents of carboxyl group.     

Metal–organic framework (UiO‐66)‐dispersed polyurethane composite films for the decontamination of methyl paraoxon

Polyurethane (PU) composite films containing UiO‐66 were prepared for the decontamination of methyl paraoxon (MPO), an organophosphate‐type nerve agent simulant. Waterborne PU dispersions were synthesized by changing the type of polyol to improve the miscibility with UiO‐66. Depending on the size of the polyol, the PU films had different surface free energy, flexibility and compatibility with UiO‐66. UiO‐66 was well dispersed in PU films when the flexibility of the films increased. The tensile strength of the UiO‐66/PU composite films gradually increased from 7.5 to 11.3 MPa with increasing UiO‐66 content, but the elongation decreased from 781 to 120%. The decomposition of MPO by the UiO‐66/PU composite films increased with an increase of the UiO‐66 content and hydrolysis time. In the case of the 21.2 wt% UiO‐66/PU composite film, 48% of MPO was decomposed within 3 h. This was similar to the decomposition when using a UiO‐66 slurry (52%) under the same decomposition conditions. Unlike the UiO‐66 slurry, the 21.2 wt% UiO‐66/PU composite film maintained a similar MPO decomposition performance after 10 repeated experiments. © 2019 Society of Chemical Industry     

Preparation and mechanical properties of waterborne polyurethane/carbon nanotube composites

Waterborne polyurethane (WBPU) and multiwalled carbon nanotubes (CNTs) composite films with 0–4.0 wt% CNTs were prepared by ultrasonic dispersion of carboxylic acid‐functionalized CNTs in WBPU followed by emulsion casting process. The elongations at break of the WBPU/CNTs composites increase with the incorporation of CNTs. The tensile strength and crystallinity of the nanocomposite films with lower CNTs contents (<2 wt%) increase obviously; while the tensile strengths of the composites with more CNTs (≥2 wt%) decrease, in contrast to the pure PU film. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations indicated that the CNTs are uniformly dispersed in the composites incorporated with lower CNTs contents (≤1.5 wt%). However, aggregation of CNTs increased with increasing CNTs content in the WBPU/CNTs composites, causing the macrophase separation. The dispersion state of the CNTs affects the crystallinity of the PU matrix and the phase separation of the composites, which are two key factors to influence the mechanical properties of the WBPU/CNTs composites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Characterization and conductive property of polyurushiol/silver conductive coatings prepared under UV irradiation

Polyurushiol/silver (PU/Ag) composite conductive coatings were prepared from urushiol and AgNO₃ under UV irradiation by using in situ radical reduction approach. The effects of the silver nitrate loading and the irradiation time on the surface resistivity of polyurushiol/silver (PU/Ag) composite films were investigated. The result from XRD analysis showed that the formation of Ag particles, and the surface resistivity of polyurushiol/silver (PU/Ag) composite films reached the value of 0.26 Ω cm, when the content of Ag particles in composite films was 23.8 wt%, and the irradiation time 90 s. Additionally, Ag particles were well dispersed in the composite films. And the films had good thermo-stability.     

Mechanical properties, morphologies, and crystallization behavior of plasticized poly(l-lactide)/poly(butylene succinate-co-l-lactate) blends

The blends of poly(l-lactide) (PLLA) with poly(butylene succinate-co-l-lactate) (PBSL) containing the lactate unit of ca. 3 mol% and Rikemal PL710 (RKM) which is a plasticizer mainly composed of diglycerine tetraacetate were prepared by melt-mixing and subsequent injection molding. The studied RKM content of the PLLA/PBSL/RKM blends was 0-20 wt%, and the PLLA/PBSL weight ratio was 100/0 to 80/20. Although elongation at break in the tensile test did not increase by the addition of 10 wt% RKM to PLLA, the addition of a small amount of PBSL to the PLLA/RKM blend caused a considerable increase of the elongation. The SEM and DSC analyses revealed that all the PLLA/PBSL/RKM blends are immiscible blends where the PBSL particles are finely dispersed, and that there is some compatibility between PLLA-rich phase and PBSL-rich phase in the amorphous state when the RKM content is 20 wt%. As a result of investigation of the crystallization behavior by DSC and polarized optical microscopic measurements, it was revealed that the addition of RKM causes the acceleration of crystalline growth rate at a lower annealing temperature, and the addition of PBSL mainly enhances the formation of PLLA crystal nucleus.     

The morphology and mechanical properties of dynamic packing injection molded PP/PS blends

As a part of long-term project aimed at super polyolefin blends, in this work, we report the mechanical reinforcement and phase morphology of the immiscible blends of polypropylene (PP) and polystyrene (PS) achieved by dynamic packing injection molding (DPIM). The shear stress (achieved by DPIM) and interfacial interaction (obtained by using styrene-butadiene-styrene (SBS) as a compatibilizer) have a great effect on phase morphology thus mechanical properties. The shear-induced morphology with core in the center and oriented zone surrounding the core was observed in the cross-section areas of the samples. The phase inversion was also found to shift towards lower PS content under shear stress, at 70 wt% in the core and 30 wt% in the oriented zone, compared with 80 wt% for static samples (without shear). The tensile strength, tensile modules and impact strength were found largely increase by means of either shear stress or compatibilizer. The PS particle size is greatly reduced with adding of SBS, and the reduced particle size results in greater resistance to deformation, which causes the co-continuous structure at oriented zone change into droplet morphology. The morphology resulting from blending and processing was discussed based on effect of interfacial tension, shear rate, phase viscosity ratio and composition. The observed change of mechanical properties was explained based on the combined effect of phase morphology (droplet-matrix or co-continuous phase) and molecular orientation under shear stress.