Bio‐based hyperbranched polyurethane/Fe3O4 nanocomposites as shape memory materials

The bio‐based shape memory polymers have generated immense interest as advanced smart materials. Mesua ferrea L. seed oil‐based hyperbranched polyurethane (HBPU)/Fe₃O₄ nanocomposites were prepared by the in‐situ polymerization technique. The transmission electron microscopy confirmed the homogeneous distribution of the Fe₃O₄ nanoparticles in polymer matrix, whereas Fourier transform infrared spectroscopic study revealed the presence of strong interfacial interactions between them. The incorporation of Fe₃O₄ (0 to 10 wt%) into the HBPU resulted in an increase in tensile strength (5.5–15 MPa) and scratch resistance (3–6 kg). The thermo‐gravimetric analysis indicated the improvement of thermal stability (240–270°C) of the nanocomposites. The nanocomposites exhibited full shape fixity, as well as almost full shape recovery under the microwave stimulus. The shape recovery speed increased with the increase of Fe₃O₄ nanoparticles content in the nanocomposites. Thus, the studied nanocomposites might be used as advanced shape memory materials in different potential fields. Copyright © 2013 John Wiley & Sons, Ltd.     

Bio‐based high‐performance waterborne hyperbranched polyurethane thermoset

Tannic‐acid‐based low volatile organic compound‐containing waterborne hyperbranched polyurethane was prepared. In order to improve the performance, it was modified in an aqueous medium using a glycerol‐based hyperbranched epoxy and vegetable‐oil‐based poly(amido amine) at different wt%. The combined system was cross‐linked by heating at 100°C for 45 min. Fourier transform infrared spectroscopy and swelling study were used to confirm the curing. A dose‐dependent improvement of properties was witnessed for the thermoset. Thermoset with 30 wt% epoxy showed excellent improvements in mechanical properties like tensile strength (~3.4 fold), scratch hardness (~2 fold), impact resistance (~1.3 fold), and toughness (~1.7 fold). Thermogravimetric analysis revealed enhancement of thermal properties (maximum 70°C increment of degradation temperature and 8°C increment of T_g). The modified system showed better chemical and water resistance compared with the neat polyurethane. Biodegradation study was carried out by broth culture method using Pseudomonas aeruginosa as the test organism. An adequate biodegradation was witnessed, as evidenced by weight loss profile, bacterial growth curve, and scanning electron microscope images. The work showed the way to develop environmentally benign waterborne polyurethane as a high‐performance material by incorporating a reactive modifier into the polymer network. Use of benign solvent and bio‐based materials as well as profound biodegradability justified eco‐friendliness and sustainability of the modified system. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface morphology and electrical properties of polyurethane nanofiber webs spray‐coated with carbon nanotubes

Multiwalled carbon nanotubes (MWNTs) were spray‐coated on electrospun polyurethane nanofiber webs for electrical conductive application. For the effective coating of MWNTs, hyperbranched polyurethane (HBPU) was used by blending with linear polyurethane, which was synthesized in the A₂ + B₃ approach using poly(ε‐caprolactone)diol, 4,4′‐methylene bis(phenylisocynate), and castor oil. SEM measurements showed that the MWNTs could be coated well along the surface of nanofibers when the HBPU was blended in the linear polyurethane nanofibers. Blending of HBPU in the nanofibers also affected the electrical conductivity of MWNT‐coated nanofiber webs. The low electrical resistance from 20 to 400 Ω/sq was obtained for MWNT‐coated nanofiber webs and their electrical resistance decreased with an increase of spraying frequency. As a potential application of MWNT‐coated nanofiber webs, the electrical heating effect because of applied voltage was demonstrated. Copyright © 2011 John Wiley & Sons, Ltd.     

Free Radical Scavenging Magnetic Iron-Based Nanoparticles in Hyperbranched and Linear Polymer Matrices

Magnetic iron nanoparticles are attracting a great deal of research and application interest in diversified fields. In this present investigation, iron nanoparticles were prepared by a in-situ chemical reduction technique in a combination of polyaniline (PANI)-polyacrylamide (PA) and PANI-hyperbranched polyurethane (HBPU) matrices to judge the suitability of hyperbranched system. The formation of the nanoparticles in polymer matrices has been investigated by FTIR, UV, XRD, SEM and TEM studies. Narrower size with better dispersion and more stable nanoparticles were found in a hyperbranched matrix system compared to a linear one. The particle size was found to be in the range of 10–20 nm and 12–35 nm in HBPU-PANI and PA-PANI matrices, respectively. Both the nanocomposites exhibit synergistic free radical scavenging capability towards 2,2-diphenyl-1-picrylhydrazyl (DPPH). The magnetic hysteresis loop of the nanocomposites indicates the super-paramagnetic behavior. The hyperbranched system is more thermostable than the linear system by 70°C.     

Amine‐cured epoxy/clay nanocomposites. I. Processing and chemical characterization

The processing of nanocomposite materials composed of amine‐cured diglycidyl ether of bisphenol A (DGEBA) reinforced with organomontmorillonite clay is reported. A novel sample preparation scheme was used to process the modified clay in the glassy epoxy network, resulting in nanocomposites where the clay was both exfoliated and intercalated by the epoxy network. The processing scheme involves sonication of the constituent materials in a solvent, followed by solvent extraction to generate a composite with homogeneous dispersions of the nanoclay. Fourier transform infrared spectroscopy (FTIR) and Fourier transform (FT‐)Raman spectroscopy confirmed that the chemical structure of the epoxy network was not affected by the use of solvents in this processing scheme. The glass‐transition temperature, T_g, linearly increased with an increased weight ratio of the nanoclay. The microstructure of clay nanoplatelets in the composites was observed with transmission electron microscopy (TEM), wide‐angle X‐ray scattering (WAXS), and small‐angle X‐ray scattering (SAXS). It was found that the clay nanoplatelets were well‐dispersed, and were intercalated as well as exfoliated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4384–4390, 2004     

Tribological performance and thermal behavior of epoxy resin nanocomposites containing polyurethane and organoclay

A series of epoxy resin nanocomposites modified by polyurethane and organically modified montmorillonite was prepared by effectively dispersing the organically modified montmorillonite in interpenetrating polymer networks (IPNs) of epoxy and polyurethane via the sequential polymeric technique and in situ polymerization. The tribological performance of the resultant EP/PU nanocomposites was investigated by a pin‐on‐disc tester, and the results showed that adding polyurethane and organically modified clay to the EP matrix had a synergistic effect on improving tribological performance of EP/PU nanocomposites. The morphologies of the worn surface were studied by scanning electron microscopy (SEM) observations, and the results indicated that the mechanism of improving tribological performance of EP/PU nanocomposites was different from that of pure EP or pure EP/PU IPNs. The thermal behavior of these nanocomposites was also investigated by thermogravimeric analysis (TGA), and the results indicated that adding organically modified clay to the matrix remedied the deterioration of the thermal degradation temperature of the interpenetrating networks. Copyright © 2008 John Wiley & Sons, Ltd.     

Mechanical,thermal and morphological behavior of bismaleimide modified polyurethane‐epoxy IPN matrices

An intercrosslinked network of bismaleimide modified polyurethane‐epoxy systems were prepared from the bismaleimide having ester linkages, polyurethane modified epoxy and cured in the presence of 4,4′‐diaminodiphenylmethane. Infrared spectral analysis was used to confirm the grafting of polyurethane into the epoxy skeleton. The prepared matrices were characterized by mechanical, thermal and morphological studies. The results obtained from the mechanical and thermal studies reveal that the incorporation of polyurethane into the epoxy skeleton increases the mechanical strength and decreases the glass transition temperature, thermal stability and heat distortion temperature. Whereas, the incorporation of bismaleimide having ester linkages into polyurethane modified epoxy systems increases the thermal stability, tensile and flexural properties and decreases the impact strength, glass transition temperature and heat distortion temperature. Surface morphology of polyurethane modified epoxy and bismaleimide modified polyurethane‐epoxy systems were studied using scanning electron microscopy. Copyright © 2003 John Wiley & Sons, Ltd.     

Vegetable oil-based flame retardant epoxy/clay nanocomposites

Flammability of epoxy appears to be one of the greatest threats and hence limits its advanced applications. The present investigation, therefore, reports on vegetable oil-based self-extinguishing epoxy/clay nanocomposites for the first time. These nanocomposites were prepared by the ex-situ technique using mechanical shearing and ultrasonication at different loadings (1, 2.5 and 5 wt%) of nano-clay. Monoglyceride of Mesua ferrea L. seed oil, bisphenol-A and tetrabromobisphenol-A based epoxy resin was used as the matrix. XRD, TEM, SEM, FTIR and rheological studies confirmed partially exfoliated nanocomposites formation. The study demonstrates two fold improvements of tensile strength and scratch hardness, three-fold increase in adhesive strength and 20 units increase in gloss value without any change in impact resistance through nanocomposite formation. TG studied confirmed the enhancement of thermal stability of the nanocomposite by 25 °C. The limiting oxygen index values and UL 94 test indicated the self-extinguishing characteristic of the nanocomposites.     

Bio-based thermostable, biodegradable and biocompatible hyperbranched polyurethane/Ag nanocomposites with antimicrobial activity

The enhanced thermal and antimicrobial activity of silver nanoparticles prompts their uses in many medical devices. Mesua ferrea L. seed oil based antimicrobial biocompatible hyperbranched and linear polyurethane/Ag nanocomposites have been prepared in dimethylformamide without using any extra reducing agent. Formation of the stable and well-dispersed Ag nanoparticles was confirmed by ultra violet, X-ray diffractometeric, transmission electron microscopic and Fourier transform infra-red spectroscopic analyses. The enhancement of properties like thermal stability by (46-53)°C and 42 °C, tensile strength to ∼170% and ∼180% for hyperbranched and linear polyurethanes respectively was observed by the formation of nanocomposites. The cytocompatibility test based on the inhibition of RBC hemolysis showed that the materials lack cytotoxicity. The nanocomposites showed biodegradability as conferred from the bacterial degradation. Dose dependent excellent antibacterial activity of the nanocomposites against Gram positive (Staphylococcus aureus) and Gram negative (Escherichia coli) bacteria and antifouling activity against Candida albicans was observed.     

The influence of reactive organoclay on a biorenewable castor oil‐based polyurethane prepolymers toughened polylactide nanocomposites

Polylactide (PLA) is the most extensively reviewed and utilized biodegradable and renewable thermoplastic polyester, with potential to replace conventional petroleum‐based polymeric materials. To improve the toughness of PLA, castor oil‐based polyurethane prepolymer (COPUP) toughened PLA nanocomposites were prepared via the melt mixing process and investigated for its mechanical, thermal and morphological properties. X‐ray diffraction and transmission electron microscopy studies revealed the formation of polymer blend nanocomposites. Mechanical tests revealed optimum performance characteristics at PLA/COPUP ratio of 70:30. Further, loading of the organoclay showed higher tensile strength and modulus of the blend nanocomposites as compared to optimized blend. The morphological results indicated that the surface roughness increases as a function of the organoclay incorporation. Thermogravimetric measurements reveal that the thermal stability of the blend increases with the incorporation of organoclay. The improved mechanical properties along with its biodegradability might lead to new industrial and biomedical applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Fabrication of high thermal stable cured novolac/Cloisite 30B nanocomposites by chemical modification of resin structure

Cloisite 30B as a modified kind of nanoclay was utilized for the formation of 3D network based on novolac resin with high thermal stable properties. Two types of phenolic resins including neat novolac (NR) and modified novolac resin were used to create a compatible matrix with nanoclay. For this purpose, NR modified with (3‐chloropropyl)triethoxysilane (CPTES) to form SiNR. For improvement of thermal behaviors, Cloisite 30B was dispersed in matrix via ultrasonic waves and cured with hexamethylenetetramine (HMTA) to form 3D network. X‐ray diffraction (XRD) analysis was used to measure the d‐spacing in intercalated systems and results indicated the optimum amount of clay for appropriate thermal properties. Investigation of the thermal properties of the samples by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the presence of Cloisite 30B in matrix resulted in much higher thermal stability and char yield with respect to modification of novolac resin originated from formation of 3D Si–O–Si network. Also, cured modified resin and its nanocomposites showed much higher thermal stability than cured NR and its nanocomposites. Such nanocomposite materials with high thermal stability have potential applications in advanced fields such electronic, industrial molds, coatings, adhesives, and aerospace composites.     

Recovery stress and work output in hyperbranched poly(ethyleneimine)‐modified shape‐memory epoxy polymers

In this study a series of hyperbranched modified shape‐memory polymers were subjected to constrained shape recoveries in order to determine their potential use as thermomechanical actuators. Materials were synthesized from a diglycidyl ether of bisphenol A as base epoxy and a polyetheramine and a commercial hyperbranched poly(ethyleneimine) as crosslinker agents. Hyperbranched polymers within the structure of the shape‐memory epoxy polymers led to a more heterogeneous network that can substantially modify mechanical properties. Thermomechanical and mechanical properties were analyzed and discussed in terms of the content of hyperbranched polymer. Shape‐memory effect was analyzed under fully and partially constrained conditions. When shape recovery was carried out with fixed strain a recovery stress was obtained whereas when it was carried out with a constraining stress the material performs mechanical work. Tensile tests at Tg^E′ showed excellent values of stress and strain at break (up to 15 MPa and almost 60%, respectively). Constrained recovery performances revealed rapid recovery stress generation and unusually high recovery stresses (up to 7 MPa) and extremely high work densities (up to 750 kJ/m³). The network structure of shape‐memory polymers was found to be a key factor for actuator‐like applications. Results confirm that hyperbranched modified‐epoxy shape memory polymers are good candidates for actuator‐like shape‐memory applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1002–1013     

Thermally conductive and electrically insulative nanocomposites based on hyperbranched epoxy and nano‐Al2O3 particles modified epoxy resin

Novel epoxy nanocomposites based on a diglycidyl ether of bisphenol A (DGEBA) epoxy, an epoxy functionalized hyperbranched polymer (HTTE) and nano‐Al₂O₃ were synthesized with the aim of determining the effect of the nano‐Al₂O₃ particles and HTTE on the structure and properties of epoxy nanocomposites. The mechanical properties, thermal conductivity, bulk resistivity, and thermal stability of the nano‐Al₂O₃/HTTE/DGEBA ternary composites were evaluated and compared with the corresponding matrix. The improvement in impact properties of these nanocomposites was explained in terms of fracture surface analysis by SEM. The results indicate that the incorporation of nanoparticles and hyperbranched epoxy effectively improved the toughness of epoxy composites without sacrificing thermal conductivity and bulk resistivity compared to the neat epoxy and Al₂O₃/DGEBA, obtaining a well dispersion of nanoparticles in epoxy matrix and solving the drawbacks for single fillers filled epoxy nanocomposite. Copyright © 2010 John Wiley & Sons, Ltd.     

Exploitation of introducing of catalytic centers into layer galleries of layered silicates and related epoxy nanocomposites. I. Epoxy nanocomposites derived from montmorillonite modified with catalytic surfactant‐bearing carboxyl groups

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo‐montmorillonite (O‐MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The intercalation and exfoliation behavior of the epoxy nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The curing behavior and thermal property were investigated by in situ Fourier transform infrared spectroscopy and DSC, respectively. The results showed that MMT could be highly intercalated by acidified CAB, and O‐MMT could be easily dispersed in epoxy resin to form intercalated/exfoliated epoxy nanocomposites. When the O‐MMT loading was lower than 8 phr (relative to 100 phr resin), exfoliated nanocomposites were achieved. The glass‐transition temperatures (T_g's) of the exfoliated nanocomposite were 20 °C higher than that of the neat resin. At higher O‐MMT loading, partial exfoliation was achieved, and those samples possessed moderately higher T_g's as compared with the neat resin. O‐MMT showed an obviously catalytic nature toward the curing of epoxy resin. The curing rate of the epoxy compound increased with O‐MMT loading. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1192–1198, 2004     

Intercalated clay nanocomposites: Morphology,mechanics, and fracture behavior

Intercalated nanocomposites of modified montmorillonite clays in a glassy epoxy were prepared by crosslinking with commercially available aliphatic diamine curing agents. These materials are shown to have improved Young's modulus but corresponding reductions in ultimate strength and strain to failure. The results were consistent with most particulate‐filled systems. The macroscopic compressive behavior was unchanged, although the failure mechanisms in compression varied from the unmodified samples. The fracture toughness of these materials was investigated and improvements in toughness values of 100% over unmodified resin were demonstrated. The fracture‐surface topology was examined using scanning electron and tapping‐mode atomic force microscopies and shown to be related to the clay morphology of the system. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1137–1146, 2001     

Nanoclay modified silica phenolic composites: mechanical properties and thermal response under simulated atmospheric re‐entry conditions

Ablative nanocomposites based on nanoclay‐dispersed addition curable propargylated phenolic novolac (ACPR) resin, reinforced with chopped silica fiber, were investigated for their thermal response behavior under simulated heat flux conditions corresponding to typical atmospheric re‐entry conditions. Organically modified nanoclay (Cloisite 30B) was incorporated to different extents (1–10%) in the ACPR resin matrix containing silica fiber to form the composite. The composites displayed optimum mechanical properties at around 3 wt% of nanoclay loading. The resultant composites were evaluated for their ablative characteristics as well as mechanical, thermal and thermo‐physical properties. The reinforcing effect of nanoclay was established and correlated to the composition. The mechanical properties of the composites and its pyrolysed product improved at moderate nanoclay incorporation. Plasma arc jet studies revealed that front wall temperature is lowered by 20°C and that at backwall by 10–13°C for the 3 wt% nanoclay‐incorporated composites due to impedance by nanoclay for the heat conduction. Nanoclay diminished the coefficient of thermal expansion by almost 50% and also reduced the flammability of the composites. The trend in mechanical properties was correlated to the microstructural morphology of the composites. The nanomodification conferred better strength to the pyrolysed composites. Copyright © 2014 John Wiley & Sons, Ltd.     

Polymeric Nanocomposites of Polyurethane Block Copolymers and Functionalized Multi‐Walled Carbon Nanotubes as Crosslinkers

Summary: We report on a new route to synthesize polymeric carbon nanotube‐polyurethane (PU) nanocomposites. Multi‐walled carbon nanotubes (MWNTs) functionalized by chemical modification were incorporated as a crosslinker in prepolymer, which was prepared from a reaction of 4,4′‐methylene bis(phenylisocyanate) and poly(ε‐caprolactone)diol. The reinforcing effect of carbon nanotubes in crosslinked MWNT‐PU nanocomposites was more pronounced as compared to that in conventional MWNT‐PU nanocomposites. The optimum content of chemically modified MWNTs for crosslinking with polyurethane was determined to be approximately 4 wt.‐% in our samples, based on observation of a NCO peak in FT‐IR spectroscopy. MWNT‐crosslinked polyurethane containing 4 wt.‐% modified MWNTs showed the highest modulus and tensile strength among the composites and pure PU. The presence of functionalized MWNTs in the polymeric nanocomposite yielded enhancement in the thermal stability due to crosslinking of the MWNTs with PU.

Possible configuration for MWNT‐PU nanocomposite molecules and FT‐IR spectra of samples obtained during reaction of prepolymer with functionalized MWNTs (second step).     

Preparation and Characterization of Epoxy/Inorganic Anti‐electrostatic Nanocomposites Using Submicrometer Al(OH)3 and Colloid Al2O3

New organic‐inorganic hybrid materials and their anti‐electrostatic hybrid membranes are prepared via sol‐gel process. The polycondensation of epoxy oligomers and AEAPS/Al₂O₃ complexes which are organically surface modified submicrometer aluminum trihydroxide inorganic fillers with an active aminoterminal silane coupling agent, N‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane (AEAPS), are performed. AEAPS enhances the interfacial interactions between the inorganic fillers and epoxy polymers. Meanwhile, this coupling agent maintains well dispersion of fillers in these composites. To improve the mechanical strength and thermal stability, pyromellitic dianhydride (PMDA) is used as curing agent. These hybrid films prepared from this method have excellent physical properties, such as UV‐shielding, high transmission in visible resign (> 85%), high hardness (7～8H) , high adhesive force (7～8) and low relative surface resistance (9.71 × 10¹¹～1.26 × 10¹⁰ Ω/cm²) with anti‐electrostatic characters. For thermal resistance, the best Td value of epoxy/PMDA/AEAPS/Al₂O₃ is 378.6 °C which is 85.4 °C higher than that of neat epoxy resin. Physical properties of these materials are almost the same as those of the nanocomposites prepared from expensive colloid Al₂O₃. Evidences from TEM micrograph show that the inorganic additives are dispersed evenly in organic matrix with nanometer scale.     

Application of Modified Natural Oils as Reactive Diluents for Epoxy Resins

Bisphenol A based low-molecular-weight epoxy resin was modified with epoxidized soybean oil, which exhibit viscosity reducing ability comparable to commercial grade active diluents. The studied compositions showed a non-Newtonian rheological behavior, typical for Bingham liquids. The values of the flow index (n) and the consistency index (k) for the compositions tested in the temperature range 25–65 °C were calculated from the Ostwald-de Waele rheological model and were used to calculate the flow-activation energy (E_a) using the Arhenius equation. Studies of co-crosslinking of mixed oil-resin compositions using isophorone diamine showed essential decrease of the reaction heat and peak maximum temperature. Mechanical properties, thermal stability, water absorption and chemical resistance of the epoxy resin modified with natural oil, were also investigated. Compositions of epoxy resin Ruetapox 0162, modified with the oil diluent, preserved very good mechanical properties of the epoxy resins and demonstrated relatively low water absorption as well as high chemical resistance. The compositions displayed even higher impact strength than pure epoxy resin due to plasticizing effect of the built-in oil. Compositions with the high contents (up to 60 weight %) of the oil were flexible materials with fast elastic recovery.