Composites of carbon nanofibers and thermoplastic polyurethanes with shape‐memory properties prepared by chaotic mixing

Composites of carbon nanofibers (CNFs), oxidized carbon nanofibers (ox‐CNFs), and shape‐memory thermoplastic polyurethane (TPU) were prepared in a chaotic mixer and their shape‐memory properties evaluated. The polymer was synthesized from 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol chain extender, and semicrystalline poly(ε‐caprolactone) diol soft segments. The shape‐memory action was triggered by both conductive and resistive heating. It was found that soft segment crystallinity and mechanical reinforcement by nanofibers produced competing effects on shape‐memory properties. A large reduction in soft segment crystallinity in the presence of CNF and stronger mechanical reinforcement by well‐dispersed ox‐CNF determined the shape‐memory properties of the respective composites. It was found that the maximum shape recovery force, respectively, 3 and 4 MPa, was obtained in the cases of 5 and 1 wt% CNF and ox‐CNF, respectively, compared with ～1.8 MPa for unfilled TPU. The degree of soft segment and hard segment phase separation and thermal stability of the composites were analyzed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers.     

Characterization of nanocellulose‐ reinforced shape memory polyurethanes

BACKGROUND: Shape memory polymers are capable of fixing a transient shape and of recovering their original dimensions by the application of an external stimulus. Their major drawback is their low stiffness compared to smart materials based on metals and ceramics. To overcome this disadvantage, nanocellulose was utilized as reinforcement. RESULTS: Composites were prepared by casting stable nanocellulose/segmented polyurethane suspensions. The heat of melting of the polyurethane soft segment phase increased on cellulose addition. Composites showed higher tensile modulus and strength than unfilled films (53% modulus increase at 1 wt% nanocellulose), with higher elongation at break. Creep deformation decreased as cellulose concentration increased (36% decrease in 60‐minute creep by addition of 1 wt% nanocellulose). The nanocomposites displayed shape memory properties equivalent to those of the neat polyurethane, with recoveries of the order of 95% (referred to second and further cycles). CONCLUSIONS: It is possible to markedly improve the rigidity of shape memory polymers by adding small amounts of well‐dispersed nanocellulose. However, this improvement did not have substantial effects on the material shape fixity or recovery. Shape memory behavior seems to continue to be controlled by the polymer properties. Copyright © 2007 Society of Chemical Industry     

Significantly improving electro‐activated shape recovery performance of shape memory nanocomposite by self‐assembled carbon nanofiber and hexagonal boron nitride

This study presents two effective approaches to significantly improve the electro‐thermal properties and electro‐activated shape recovery performance of shape memory polymer (SMP) nanocomposites that are incorporated with carbon nanofibers (CNFs) and hexagonal boron nitrides (h‐BNs), and show Joule heating triggered shape recovery. CNFs were self‐assembled and deposited into buckypaper form to significantly improve the electrical properties of SMP and achieve the shape memory effect induced by electricity. The h‐BNs were either blended into or self‐assembled onto CNF buckypaper to significantly improve the thermally conductive properties and electro‐thermal performance of SMPs. Furthermore, the shape recovery behavior and temperature profile during the electrical actuation of the SMP nanocomposites were monitored and characterized. It was found that a unique synergistic effect of CNFs and h‐BNs was presented to facilitate the heat transfer and accelerate the electro‐activated shape recovery behavior of the SMP nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40506.     

Development of novel conducting composites of linseed‐oil‐based poly(urethane amide) with nanostructured poly(1‐naphthylamine)

Novel conducting polymer composites of linseed‐oil‐based poly(urethane amide) (LPUA) were synthesized using nanostructured poly(1‐naphthylamine) (PNA). The combination of the electrically conducting PNA with LPUA was accomplished through different weight percent loadings (0.5–2.5 wt%) of the conducting polymer. The particle size of the nanocomposite was determined using transmission electron microscopy and was found to be in the range 17–27 nm. Intermolecular hydrogen bonding between the two polymers and formation of urea linkages were confirmed by Fourier transform infrared spectroscopy. The electrical conductivity of the nanostructured conducting composites at 2.5 wt% loading was found to be comparable to that reported for polyaniline (PANI)/polyurethane at 30 wt% loading of PANI. This shows the superior properties of PNA and its potential for application in anti‐static as well as corrosion‐protective coatings. The present method of formulation of composites using an oil‐based polymer matrix is useful and economically feasible in the sense that a great variety of oil‐based polymer matrices can be used to form composites that are ecologically safe and exhibit properties similar to commercial polymers. Copyright © 2007 Society of Chemical Industry     

Mechanical recycling of nanocellulose containing multilayer packaging films

The aim of this study was to demonstrate mechanical recycling of low density polyethylene (LDPE) films coated with a thin layer of cellulose nanofibrils (CNFs). CNF acts as an effective barrier against oxygen and mineral oil residues. Two different CNF grades were tested, and both were applied onto plasma activated LDPE film using a pilot coating line. The coated films were shredded with the help of liquid nitrogen, compacted and compounded with virgin LDPE and compatibilizer, and processed into cast films and injection molded test specimens. The CNF coatings were completely blent as microscale agglomerates in the LDPE matrix. The effect of these agglomerates on the barrier and heat sealing properties was statistically insignificant compared to recycled uncoated LDPE. The mechanical properties were only moderately changed. CNF‐coated LDPE films can therefore be recycled back into films without sacrificing the characteristic properties of the base polymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46237.     

Hyperbranched‐modified epoxy thermosets: Enhancement of thermomechanical and shape‐memory performances

In this study a complete characterization of the thermomechanical and shape‐memory properties of epoxy shape‐memory polymers modified with hyperbranched polymer and aliphatic diamine was performed. Focusing on the mechanical properties that are highly desirable for shape‐memory polymers, tensile behavior until break was analyzed at different temperatures and microhardness and impact strength were determined at room temperature. As regards shape memory performance, the materials were fully characterized at different programming temperatures to study how this influenced the recovery ratio, fixity ratio, shape‐recovery velocity, and switching temperature. Tensile testing revealed a peak in deformability and in the stored energy density at the onset of the glass transition temperature, demonstrating that this is the best programming temperature for obtaining the best shape‐memory performances. The Young's moduli revealed more rigid structures in formulations with higher hyperbranched polymer content, while microhardness showed higher values with increasing hyperbranched polymer content due to the increased crosslinking density. Impact strength was greatly improved as the aliphatic diamine content increases due to the energy dissipation capability of its flexible structure. As regards the shape‐memory properties, increasing the programming temperature has a minor effect on formulations with a lower hyperbranched polymer content and worsens these properties when the hyperbranched polymer content is increased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44623.     

Polyurethane/conducting carbon black composites: Structure,electric conductivity,strain recovery behavior,and their relationships

The polyurethane composites with conducting carbon black (CB) were prepared by a solution‐precipitation process, which was followed by melt compression molding. The polyurethane used has good shape memory effect. The morphology of CB fillers in polyurethane matrix and the resulting conductivity of the composites were investigated. It has been found that CB fillers exist in the forms of aggregates. The percolation threshold is achieved at the CB concentration of 20 wt %. The presence of CB fillers decreases the degree of crystallinity of polycaprolactone (PCL) soft segments of the polyurethane. However, the composites still have enough soft‐segment crystals of polyurethane to fulfil the necessary condition for the shape memory properties. Dynamic mechanical data show that CB is an effective filler for the reinforcement of the polyurethane matrix, but does not deteriorate the stable physical cross‐link structure of the polyurethane, which is necessary to store the elastic energy in the service process of the shape memory materials. Addition of CB reinforcement in the polyurethane has influenced the strain recovery properties, especially for those samples with CB concentrations above the percolation threshold. The response temperature of the shape memory effect T_r has not been affected too much. Strain fixation S_f, which expresses the ability of the specimens to fix their strain, has been improved in the presence of the CB fillers. The final recovery rates R_f and strain recovery speeds V_r of the shape memory measurements, however, have decreased evidently. It is expectedly ascribed to the increased bulk viscosity as well as the impeding effect of the inter‐connective structure of CB fillers in the polymer matrix. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 68–77, 2000     

Study of nanoreinforced shape memory polymers processed by casting and extrusion

Multi‐walled carbon nanotubes (CNTs) and cellulose nanofibers (CNFs) reinforced shape memory polyurethane (PU) composite fibers and films have been fabricated via extrusion and casting methods. Cellulose nanofibers were obtained through acid hydrolysis of microcrystalline cellulose. This treatment aided in achieving stable suspensions of cellulose crystals in dimethylformamide (DMF), for subsequent incorporation into the shape memory matrix. CNTs were covalent functionalized with carboxyl groups (CNT‐COOH) and 4,4′‐methylenebis (phenylisocyanate) (MDI) (CNT‐MDI) to improve the dispersion efficiency between the CNT and the polyurethane. Significant improvement in tensile modulus and strength were achieved by incorporating both fillers up to 1 wt% without sacrificing the elongation at break. Electron microscopy was used to investigate the degree of dispersion and fracture surfaces of the composite fibers and films. The effects of the filler (type and concentration) on the degree of crystallinity and thermal properties of the hard and soft segments that form the PU sample were studied by calorimetry. Overall, results indicated that the homogeneous dispersion of nanotubes and cellulose throughout the PU matrix and the strong interfacial adhesion between nanotubes and/or cellulose and the matrix are responsible for the enhancement of mechanical and shape memory properties of the composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Synthesis and properties of shape memory graphene oxide/polyurethane chemical hybrids

Graphene oxide modified chemically with allyl isocyanate (iGO) was incorporated in various amounts into acrylate‐terminated polyurethane (PU) via UV curing. The effects of this incorporation on the morphological, mechanical, dynamic mechanical, thermal and shape memory properties of the resulting hybrids were examined. The iGO nanoparticles incorporated into the PU chains acted as both multifunctional crosslinks and reinforcing fillers, and the effects were most pronounced at low iGO contents (0.5 and 1.0 wt%). Consequently, the glassy and rubbery state moduli, yield strength, glass transition temperature, shape fixity and shape recovery ratios were increased on adding up to 1 wt% iGO. At higher iGO loadings, the values of most of these properties decreased due to aggregation and the auto‐inhibition of allyl compounds. © 2013 Society of Chemical Industry     

Nanocomposites made from cellulose nanocrystals and tailored segmented polyurethanes

The effect of the addition of microcrystalline cellulose nanofibers into linear segmented polyurethanes (SPU) was investigated. The polymers were synthesized with 4,4‐methylene‐bisphenyldiisocyanate (MDI) and poly(tetramethyleneglycol) (PTMG) with 1,4‐butanediol (BD) as chain extender. The nanocrystals were introduced during the PU polymerization, which resulted in cellulose nanofibrils covalently linked to the polymer. The interactions between the cellulose nanofibrils and the matrix lead to interesting changes in the behavior of the PU, with the hard segment (HS) phase being more affected by these interactions. SPUs with different contents of HS were synthesized to better understand these effects (23 to 45 wt %). Thermal, thermo‐mechanical and mechanical characterization of the nanocomposites were performed. In general, the nanocellulose favored the phase separation between the soft and hard domains generating an upward shift in the melting temperatures of the crystalline phases, an increase in the Young's modulus and a decrease in deformation at break. Comparison of the unfilled polymer responses and that of the nanocomposites showed that by increasing cellulose content, increased dynamic storage and tensile modulus as well as melting temperatures and enthalpy of melting of the soft domains can be achieved. Addition of cellulose during the polymerization essentially erased the potential shape memory behavior originally displayed by some of the SPU. However, a sample prepared by adding the cellulose nanocrystals after the reaction showed that the mechanical properties were still improved, while the shape memory behavior of the polymer was preserved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Multi‐stimuli responsive shape memory polymers synthesized by using reaction‐induced phase separation

Thermo‐induced multishape memory polymers are a growing focus of smart materials because of its promising applications. Multishape memory effect is generally attained by using polymers with broad phase transition and multiphase polymers. The latter is of particular interest for copolymerization and polymer compositing. One requirement has to be fulfilled to achieve multishape memory effect, which is to have two reversible phase transitions. In this study, we report synthesis of polymer composite composed of strong segregated polymers by using reaction‐induced phase separation. We demonstrate the method by using polyurethane (PU) and poly(methacrylic acid) (PMAA). With adjusting the weight ratio, the polymer composites exhibit a phase spectrum from phase separation to miscible composite. The composite with PU/PMAA =3:1 demonstrated triple‐shape memory effect. Based on the results, we argued the effect of segregation on the shape memory effect for polymer composites. With the addition of PMAA, the polymer composite also exhibits pH/water‐induced shape memory effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43534.     

Effect of polyaniline surface modification of carbon nanofibers on cure kinetics of epoxy resin

Polyaniline (PANI) “nanograss” was grown on carbon nanofibers (CNFs). The cure behavior of an epoxy resin with and without unmodified CNFs or PANI modified CNFs was studied by means of non‐isothermal and isothermal differential scanning calorimetry (DSC). CNFs accelerated the reaction of epoxy and diamine. PANI surface modification further increased the reaction rate and the extent of reaction. An autocatalytic cure kinetic model was used to fit the reaction curves. It was found that activation energies of the epoxy reaction decreased in the presence of CNFs and PANI modified CNFs. The observed catalytic effect of CNF and PANI surface coating can be very useful for low temperature cure of large epoxy composite products. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Interfacial modification mechanism of nanocellulose as a compatibilizer for immiscible binary poly(vinyl alcohol)/poly(ethylene oxide) blends

We undertook this study to understand reinforcement mechanism of short cellulose nanocrystals (CNCs) and long cellulose nanofibrils (CNFs) as compatibility agents for improving the interfacial miscibility of poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO) blends. The effects of the two cellulose nanofibers on the morphological, mechanical, and thermal properties of the polymer blends were compared systematically. The light transparency, scanning electron microscopy, and Fourier transform infrared results show that nanocellulose between PVA and PEO eliminated the negative effects generated by the immiscible interface through increased hydrogen bonding. Thermogravimetric analysis and differential scanning calorimetry results show that crystalline region reorganization around the interface facilitated the shift of the polymer blends from multiple phases to a homogeneous phase. According to the Halpin‐Kardos and Quali models, we assumed that the potential for repairing the immiscible interface would have a larger effect than the potential of reinforcement. At the same concentration, polymer blends with CNCs showed greater light transparency, strength, modulus, and crystal structure than with those with CNFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45896.     

Polyaniline‐grafted polyurethane coatings for corrosion protection of mild steel surfaces

We report the superior corrosion‐resistant properties of conducting polyurethane networks of polyaniline (PANI), poly‐m‐aminophenol (PmAP), and poly‐o‐anisidine (PoA) coated on mild steel panels. These networks were prepared by blending conducting polyanilines with isocyanate‐containing prepolyurethanes. Free‐standing polyurethane films were obtained after a moisture cure for several days to ensure complete reaction of the excess isocyanate. The films were electrochemically active with conductivity in the range of 10^?2 to 10^?3 S/cm. The solution blends and formed films were characterized by infrared, ultraviolet, thermogravimetric analysis, and differential scanning calorimetry. Electrochemical corrosion studies of the coated films on mild steel panels showed excellent corrosion protection in the following order: PU‐PANI > PU‐PmAP > PU‐PoA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45806.     

Multi-functional polyurethane composites with self-healing and shape memory properties enhanced by graphene oxide

Development of shape memory polymer materials with integrated self-healing ability, shape memory property, and outstanding mechanical properties is a challenge. Herein, isophorone diisocyanate, polytetramethylene ether glycol, dimethylglyoxime, and glycerol have been used to preparation polyurethane by reacting at 80°C for 6 h. Then, graphene oxide (GO) was added and the reaction keep at 80°C for 4 h to obtain polyurethane/GO composite with self-healing and shape memory properties. Scanning electron microscopy shows that the GO sheets were dispersed uniformly in the polyurethane matrix. The thermal stability was characterized by thermogravimetric analyses. The tensile test shows that the Young's modulus of the composites increases from 38.57 ± 4.35 MPa for pure polyurethane to 95.36 ± 10.35 MPa for the polyurethane composite with a GO content of 0.5 wt%, and the tensile strength increases from 6.28 ± 0.67 to 15.65 ± 1.54 MPa. The oxime carbamate bond and hydrogen bond endow the composite good self-healing property. The healing efficiency can reach 98.84%. In addition, the composite has excellent shape memory property, with a shape recovery ratio of 88.6% and a shape fixation ratio of 55.2%. This work provides a promising way to fabricate stimulus-responsive composite with versatile functions.     

Synthesis and studies of the physical properties of polyaniline and polyurethane‐modified epoxy composites

Two series of toughened, semiconductive polyaniline (PANI)/polyurethane (PU)‐epoxy (PANI/PU‐EPOXY) nano‐composites were prepared using a conductive polymer, PANI, and PU prepolymer‐modified‐diglycidyl ether of bisphenol A (DGEBA) epoxy. First, the PU prepolymer‐modified epoxy oligomer was synthesized by a stoichiometric reaction between the terminal isocyanate groups of the PU prepolymer and the pendent hydroxyl groups of the epoxide. PU prepolymers were made either of polyester (polybutylene adipate, PBA) or polyether (polypropylene glycol, PPG) segments. The composites were characterized by thermal, morphological, mechanical, and electrical studies. Impact strength was enhanced 100% in PU (PPG 2000)‐modified composites; whereas, only ca. 30–50% increases in impact strength were observed for the other modified composites. In addition, the thermal stability of this composite proved superior to that of neat epoxy resin, regardless of a PU content at 27.5 wt%. Scanning electron microscopy (SEM) morphology study showed that the spherical PU (PPG 2000) particles (ca. 0.2–0.5 μm) dispersed within the matrix accounts for these extraordinary properties. The conductivity of the composite increased to ca. 10^?9–10^?3 S cm^?1 upon addition of PANI when tested in the frequency range 1 kHz–13 MHz. This study demonstrated a useful way to simultaneously improve the toughness and conductivity of the epoxy composite, thus rendering it suitable for electromagnetic interference and various charge dissipation applications. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Nanoclay-tethered shape memory polyurethane nanocomposites

The study investigated shape memory properties of nanoclay-tethered polyurethane nanocomposites. Polyurethanes based on polycaprolactone (PCL) diol, methylene diisocyanate, and butane diol and their nanocomposites of reactive nanoclay were prepared by bulk polymerization in an internal mixer and the values of shape fixity and shape recovery stress were determined as function of clay content. The melting point of the crystalline soft segment was used as the transition temperature to actuate the shape memory actions. It was seen that clay particles exfoliated well in the polymer, decreased the crystallinity of the soft segment phase, and promoted phase mixing between the hard and soft segment phases. Nevertheless, the soft segment crystallinity was enough and in some cases increased due to stretching to exhibit excellent shape fixity and shape recovery ratio. A 20% increase in the magnitude of shape recovery stress was obtained with the addition of 1 wt% nanoclay. The room temperature tensile properties were seen to depend on the competing influence of reduced soft segment crystallinity and the clay content. However, the tensile modulus measured at temperatures above the melting point of the soft segment crystals showed continued increases with clay content.     

Bio‐based hyperbranched polyurethane/multi‐walled carbon nanotube nanocomposites as shape memory materials

Mesua ferrea L. seed oil based hyperbranched polyurethane/multi‐walled carbon nanotube nanocomposites were prepared by solution polymerization technique. The multi‐walled carbon nanotubes were modified with the polyoxyethylene octyl phenyl ether (Triton X‐100). The transmission electron microscopy and Fourier transform infrared spectroscopic study revealed the homogeneous distribution of the multi‐walled carbon nanotubes in the polymer matrix and the presence of strong interfacial interaction between them, respectively. The tensile strength (5.5–21.5 MPa) and scratch resistance (3–6.1 kg) increase with the increase of the content of carbon nanotubes (0 to 2 wt%). The thermo‐gravimetric analysis result showed the increment of thermal stability (240–275°C) of the nanocomposites. All the prepared nanocomposites exhibited the excellent shape fixity and shape recovery. The shape recovery time decreases (127–73 s) with the increase of the concentration of carbon nanotubes in the nanocomposites. Thus the prepared nanocomposites might be utilized as advanced shape memory applications. POLYM. COMPOS., 35:636–643, 2014. © 2013 Society of Plastics Engineers     

A facile approach to fabricate waterborne,nanosized polyaniline‐graft‐(sulfonated polyurethane) as environmental antistatic coating

Waterborne polyurethane (WPU) has been intensively utilized as host materials for intrinsic conducting polymers. However, the stability and compatibility between polyaniline (PANI) and WPU remain a challenge for their composites. In this research, anionic–nonionic sulfonated waterborne polyurethane (SWPU) is adopted as matrix to prepare nanosized PANI‐g‐SWPU dispersions through chemical graft polymerization method, and the stability mechanism is systematically investigated. The PANI‐g‐SWPU dispersion is endowed with much higher stability and no PANI precipitation is detected after storage for 1 year when the PEG molecular weight is 1000 and R value is 1.2. The surface resistivity reaches the minimum when the graft time is 2.5 h, pH value is 2, n(APS)/n(aniline) is 1, and the aniline content is 20 wt %. And the resistivity of the coated paper reaches 1.39 Ω cm, indicating that the as‐prepared PANI‐g‐SWPU dispersion can be directly used as the antistatic coatings, which is also suitable for large scalable production. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45412.     

The influence of PVP on the synthesis and electromagnetic properties of PANI/PVP/CIP composites

Polyaniline/carbonyl iron powder (PANI/CIP) composites with core‐shell structure were synthesized via in situ polymerization in aqueous solution of polyvinylpyrrolidon (PVP). The micromorphology, structure, and microwave absorbing property of the PANI/PVP/CIP composites were characterized by scanning electron microscopy, fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), and vector network analysis. And, the modified mechanism of PVP on polymerization was discussed. The research showed that the presence of PVP was conducive to not only dispersion of CIP but also the formation coated well with PANI. PANI/CIP composites that were decorated by PVP have obviously improved on wave absorbing property compared with the composites which were synthesized without PVP. With the concentrations of 10 wt% PVP, the PANI/PVP/CIP composites show best microwave absorption, which the minimum reflection loss (RL) was −26.4 dB at 38.1 GHz and the corresponding thickness was 0.9 mm; for a thickness of 1.1 mm, an RL exceeding −10 dB was obtained in the frequency range of 27.6–39.0 GHz. POLYM. COMPOS., 36:1799–1806, 2015. © 2014 Society of Plastics Engineers