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1.
BACKGROUND: The technological development of poly(ε‐caprolactone) (PCL) is limited by its short useful lifespan, low modulus and high crystallinity. There are a few papers dealing with the crystallization behavior of carbon nanotube‐reinforced PCL composites. However, little work has been done on the crystallization kinetics of melt‐compounded PCL/multiwalled carbon nanotube (MWNT) nanocomposites. In this study, PCL/MWNT nanocomposites were successfully prepared by a simple melt‐compounding method, and their morphology and mechanical properties as well as their crystallization kinetics were studied. RESULTS: The MWNTs were observed to be homogeneously dispersed throughout the PCL matrix. The incorporation of a very small quantity of MWNTs significantly improved the storage modulus and loss modulus of the PCL/MWNT nanocomposites. The nonisothermal crystallization behavior of the PCL/MWNT nanocomposites exhibits strong dependencies of the degree of crystallinity (Xc), peak crystallization temperature (Tp), half‐time of crystallization (t1/2) and Avrami exponent (n) on the MWNT content and cooling rate. The MWNTs in the PCL/MWNT nanocomposites exhibit a higher nucleation activity. The crystallization activation energy (Ea) calculated with the Kissinger model is higher when a small amount of MWNTs is added, then gradually decreases; all the Ea values are higher than that of pure PCL. CONCLUSION: This paper reports for the first time the preparation of high‐performance biopolymer PCL/MWNT nanocomposites prepared by a simple melt‐compounding method. The results show that the PCL/MWNT nanocomposites can broaden the applications of PCL. Copyright © 2008 Society of Chemical Industry  相似文献   

2.
Poly(ε‐caprolactone) (PCL) was melt compounded with “Bucky gels”‐like mixture that prepared by grinding multiwalled carbon nanotubes (MWNTs) and ionic liquids (ILs). Raman spectrum showed the significant interaction between ILs and MWNTs. The dielectric behavior of PCL nanocomposites based on unmodified and IL‐modified MWNTs was studied from 40 Hz to 30 MHz. The addition of ILs significantly enhanced the dielectric property of PCL/IL/MWNT ternary nanocomposites, which was much higher than that of the sum of PCL/IL with PCL/MWNT binary nanocomposites. The dielectric properties of PCL/IL/MWNT nanocomposites were mainly influenced by ILs in low frequency and were dominated by MWNTs in high frequency. SEM results revealed that a more uniform and fine dispersion of MWNTs were achieved throughout the PCL matrix because of ILs. The addition of ILs in nanocomposites changed the crystallinity of PCL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40231.  相似文献   

3.
Polyamide6 (PA6)/acrylonitrile butadiene styrene copolymer (ABS) blends with unmodified multiwall carbon nanotubes (MWNTs) were prepared via melt‐blending in a conical twin‐screw micro‐compounder with varying melt‐mixing time. To improve the state of dispersion of MWNTs, non‐covalent organic modifiers for MWNTs have been utilized: sodium salt of 6‐amino hexanoic acid (Na‐AHA) and 1‐pyrene‐carboxaldehyde (PyCHO). PA6/ABS blends with MWNTs have shown a phase morphology transition from ‘matrix‐dispersed droplet’ type to ‘co‐continuous’ type as a function of melt‐mixing time with the exception of 40/60 PA6/ABS blend with PyCHO‐modified MWNTs. Non‐isothermal crystallization studies revealed the heterogeneous nucleating action of MWNTs through the presence of double crystallization exothermic peaks (at ~192°C and >200°C) while pure PA6 shows bulk crystallization peak at ~192°C. 40/60 and 60/40 (wt/wt) PA6/ABS blends with 5 wt% unmodified MWNTs exhibited electrical conductivity values of ~3.9 × 10?11 S/cm and ~4.36 × 10?6 S/cm, respectively. A significant enhancement in electrical conductivity was observed with Na‐AHA and PyCHO‐modified MWNTs (order of ~10?6 and ~10?4 S/cm, respectively). POLYM. ENG. SCI., 55:429–442, 2015. © 2014 Society of Plastics Engineers  相似文献   

4.
Multiwall carbon nanotubes (MWNTs) were melt‐mixed in polyamide 6 (PA6) and acrylonitrile–butadiene–styrene (ABS) copolymer blends using a simultaneous mixing protocol in order to investigate the state of dispersion of MWNTs in PA6/ABS blends. The blend composition was varied from 40/60 (wt/wt) to 60/40 (wt/wt) in PA6/ABS blends, which showed ‘co‐continuous’ morphology in the presence of MWNTs. State of dispersion of MWNTs in these blends was assessed through bulk electrical conductivity measurements, morphological analysis, solution experiments, and UV‐vis spectroscopic analysis. MWNTs were subsequently modified with a novel organic modifier, sodium salt of 6‐aminohexanoic acid (Na‐AHA), to improve the state of dispersion of MWNTs. Blends with unmodified MWNTs exhibited the DC electrical conductivity in the range ~10?11 to ~10?5 S/cm, whereas blends with Na‐AHA‐modified MWNTs exhibited DC electrical conductivity in the range ~10?7 to ~10?5 S/cm. The reduction in MWNTs ‘agglomerate’ size (~73.7 μm for 40/60 blend with unmodified MWNTs to ~59.9 μm in the corresponding blend with Na‐AHA‐modified MWNTs) was observed through morphological analysis. The rheological studies showed increased complex viscosity and storage moduli in lower frequency region in case of blends with Na‐AHA‐modified MWNTs confirming a refined ‘network‐like’ structure of MWNTs. POLYM. ENG. SCI., 55:443–456, 2015. © 2014 Society of Plastics Engineers  相似文献   

5.
The effect of the polymeric crosslink density on the thermal conductivity of an epoxy nanocomposite was investigated by adding two different diamine‐functionalized multiwalled carbon nanotubes (diamine‐MWNTs) to the epoxy resin as co‐curing agents and conducting fillers. Tetramethylenediamine (TMDA)‐MWNTs resulted in an epoxy nanocomposite with a higher crosslink density than octamethylenediamine (OMDA)‐MWNTs. Interestingly, epoxy/TMDA‐MWNT nanocomposites under 1.5 wt % nanotube concentration, showed a higher thermal conductivity than an epoxy/OMDA‐MWNT nanocomposite with the same concentration of nanotubes. In contrast, for higher diamine‐MWNT concentrations (over 2.0 wt %), the thermal conductivity of the epoxy/OMDA‐MWNT nanocomposite was higher than that with TMDA‐MWNTs. We observed that for low MWNT concentrations, where a percolating network was not formed, a high crosslink density enhanced the thermal conductivity via phonon transport. However, for high MWNT concentrations, a high crosslink density hinders the formation of a percolating network and lowers the thermal conductivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44253.  相似文献   

6.
So far, the reported content of multiwall carbon nanotubes (MWNTs) in polymer/MWNTs nanocomposites is usually above 0.1 wt %. In this article, we will report our work on the study of the morphology, crystallization, and mechanical properties of poly(ethylene terephthalate) (PET)/MWNTs nanocomposites prepared by in situ polymerization with very low content of MWNTs (from 0.01 to 0.2 wt %). Well‐dispersed MWNTs with a big network throughout PET matrix were observed by SEM. The very small amount of MWNTs displayed a great nucleating effect on the PET crystallization. The crystallization temperature was improved for 6.4°C by using only 0.01 wt % MWNTs. The decreased chain mobility of PET by adding MWNTs was evident by the formation of imperfect or smaller/thinner crystallites with low melting temperature. An increased storage modulus was also achieved for the nanohybirds with MWNT content less than 0.05 wt %. Our result indicates that using very low content MWNTs (less than 0.1 wt %) is a simple way to achieve good dispersion, yet with remarkable enhancement for polymer/MWNTs modification. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3695–3701, 2007  相似文献   

7.
Composites of polyaniline (PANI) nanorods and multiwalled carbon nanotubes (MWNTs) coated with PANI were prepared by in situ polymerization with perchloric acid as a dopant. Transmission electron microscopy images showed that the coexisting composites of PANI nanorods and MWNTs coated with PANI were formed at low MWNT contents. The interaction between MWNTs and PANI was proved by Fourier transform infrared and ultraviolet–visible spectra. The electrical conductivity of a dedoped PANI/MWNT composite with a 16.3 wt % concentration of MWNTs reached 3.0 × 10?3 S/cm, which was 6 orders of magnitude higher than that of dedoped PANInanorods. The results also showed that coexisting composites of PANI nanorods and MWNTs coated with PANI had high electrochemical activity and good cyclic stability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

8.
A novel cyclic initiator was synthesized from dibutyl tin(IV) oxide and hydroxyl‐functionalized multiwalled carbon nanotubes (MWNTs) and was used to initiate the ring‐opening polymerization of cyclic butylene terephthalate oligomers to prepare poly(butylene terephthalate) (PBT)/MWNT nanocomposites. The results of Fourier transform infrared and NMR spectroscopy confirmed that a graft structure of PBT on the MWNTs was formed during the in situ polymerization; this structure acted as an in situ compatibilizer in the nanocomposites. The PBT covalently attached to the MWNT surface enhanced the interface adhesion between the MWNTs and PBT matrix and, thus, improved the compatibility. The morphologies of the nanocomposites were observed by field emission scanning electron microscopy and transmission electron microscopy, which showed that the nanotubes were homogeneously dispersed in the PBT matrix when the MWNT content was lower than 0.75 wt %. Differential scanning calorimetry and thermogravimetric analysis were used to investigate the thermal properties of the nanocomposites. The results indicate that the MWNTs acted as nucleation sites in the matrix, and the efficiency of nucleation was closely related to the dispersion of the MWNTs in the matrix. Additionally, the thermal stability of PBT was improved by the addition of the MWNTs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

9.
This study focuses on the electrical properties of polycarbonate (PC)/poly(ε‐caprolactone) (PCL)‐multiwall carbon nanotube (MWCNT) nanocomposites. MWCNTs were incorporated into thermoplastic PC matrix by simple melt blending using biodegradable PCL based concentrates with MWCNT loadings (3.5 wt%). Because of the lower interfacial energy between MWCNT and PCL, the nanotubes remain in their excellent dispersion state into matrix polymer. Thus, electrical percolation in PC/PCL‐MWCNT nanocomposites was obtained at lower MWCNT loading rather than direct incorporation of MWCNT into PC matrix. AC and DC electrical conductivity of miscible PC/PCL‐MWCNT nanocomposites were studied in a broad frequency range, 101?106 Hz and resulted in low percolation threshold (pc) of 0.14 wt%, and the critical exponent (t) of 2.09 from the scaling law equation. The plot of logσDC versus p?1/3 showed linear variation and indicated the existence of tunneling conduction among MWCNTs. At low MWCNT loading, the influence of large polymeric gaps between conducting clusters is the reason for the frequency dependent electrical conductivity. Transmission electron microscopy and field emission scanning electron microscopy showed that MWCNTs were homogeneously dispersed and developed a continuous interconnected network path throughout the matrix phase and miscibility behavior of the polymer blend. POLYM. ENG. SCI., 54:646–659, 2014. © 2013 Society of Plastics Engineers  相似文献   

10.
High electrochemical active free‐standing multiwalled carbon nanotube (MWNT) films have been synthesized from aniline oligomer functionalized MWNTs (MWNT‐AO), by using filtration of the acidic phosphate ester (APE) doped MWNT‐AO dispersions. The homogeneously distributed MWNTs endowed APE/MWNT films automatically releasing from the filter membrane. The sheet resistivity of MWNT‐AO (850 Ω sq?1) showed a lower value than that of carboxyl MWNTs (1273 Ω sq?1), due to the doping effect of MWNT on aniline oligomer, confirmed by the N1s X‐ray photoelectron spectrum. However, it showed a higher sheet resistivity value of 1526 Ω sq?1 after further doped by APE, because of the presence of unreacted dopant. After removing the residual insulating dopant by the vacuum filtration, the resultant APE/MWNT films showed the sheet resistivity value as low as 131 Ω sq?1. Thermogravimetric analysis showed that the MWNT loading in the film can be over than 77%, which showed the specific capacitance as high as 249 F g?1. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40259.  相似文献   

11.
Electrically conductive nanocomposites based on ethylene acrylic elastomer (AEM) and multiwalled carbon nanotube (MWNT) have been successfully prepared. Before mixing the MWNT is dispersed in ethanol in presence of ionic liquids such as 1‐methyl‐3‐octylimidazolium chloride (MOIC) and 1‐allyl‐3‐methyl imidazolium chloride (AMIC). Uniform dispersion of MWNT in the nanocomposites is achieved in presence of ionic liquid, which is confirmed by the high‐resolution transmission electron microscopic (HRTEM) microphotographs. The tensile strength increases up to 6 phr of MWNT loading and above that it decreases. However, the tensile strength increases due to the incorporation of ionic liquid assisted dispersed MWNT. It is observed from the dynamic mechanical analysis (DMA) that the storage modulus (E′) and glass transition temperature (Tg) of AEM matrix increase by incorporation of MWNT. The E′ also increases and the tan δmax marginally decreases due to the incorporation of dispersed MWNT in presence of ionic liquids. The dielectric relaxation characteristic properties of AEM/MWNT nanocomposites such as dielectric permittivity (ε′), AC conductivity (σac), impedance (Z*) have been studied as a function of frequency (101−106 Hz) in presence of ionic liquids. The ε′ and σac increase with increasing the MWNT loading due to the easy orientation of dipoles and formation of interconnected conductive networks in the nanocomposites. The electromagnetic interference shielding effectiveness (EMISE) is studied in the X‐band frequency range of 8 to 12 GHz, which significantly improved with increase in MWNT loading. POLYM. COMPOS., 37:2568–2580, 2016. © 2015 Society of Plastics Engineers  相似文献   

12.
A multiwalled carbon nanotube (c‐MWNT)/polyaniline (PANI) composite was synthesized by an in situ chemical oxidative polymerization process. With the carbon nanotube loading increased from 0 to 30 wt %, the conductivity also increased and became weakly temperature‐dependent. Fourier transform infrared spectroscopy studies showed that the synthesis by an in situ process led to effective site‐selective interactions between the quinoid ring of the PANI and the multiwalled nanotubes, facilitating charge‐transfer processes between the two components. The morphological analysis indicated that the c‐MWNTs were well dispersed and isolated, and the tubes became crowded proportionally to the weight percentage of c‐MWNTs used in the composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

13.
Poly(butylene terephthalate)/multiwalled carbon nanotubes (PBT/MWNT) nanocomposites were prepared by in situ ring‐opening polymerization of cyclic butylene terephthalate oligomers (CBT). The nonisothermal crystallization behavior of the neat PBT and the PBT/MWNT nanocomposites was analyzed quantitatively. The results reveal that the combined Avrami/Ozawa equation exhibits great advantages in describing the nonisothermal crystallization of PBT and its nanocomposites. The presence of MWNTs has the nucleation effect promoting crystallization rate for the nanocomposites, and the maximum one is observed in the nanocomposite having 0.75 wt % MWNT content. On the other hand, the addition of MWNTs has the impeding effect reducing the chain mobility and retarding crystallization, which is confirmed by the crystallization activation energies. However, the nucleation effect of MWNTs plays the dominant role in the crystallization of PBT/MWNT nanocomposites, in other words, the incorporation of MWNTs is increasing the crystallization rate of the nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40849.  相似文献   

14.
The effect of multiwall carbon nanotubes (MWNT) concentration and cooling rate on the morphological, structural and electrical properties of non‐isothermally crystallized Poly(ethylene naphthalate) nanocomposites (PEN/MWNT) was studied. PEN/MWNT nanocomposites containing 1 and 2 wt % of nanotubes were prepared by melt blending in a mini twin screw extruder. Nanocomposite samples with different degree of crystallinity (Xc) were obtained via non‐isothermally crystallization at cooling rates of 2, 10, 20, and 300°C min?1. In this study it was demonstrated that carbon nanotubes and cooling rate strongly influence morphological and structural characteristics of PEN. Calorimetric results showed that the peak crystallization temperature (Tc) of PEN nanocomposites was increased ~9° through heterogeneous nucleation with respect to pure PEN. X‐ray diffraction revealed that carbon nanotubes modify the crystalline structure of PEN favoring the formation of β‐crystals, and this effect increases with the nanotubes content. On the basis of X‐ray scattering analysis, the variation of lamellar thickness revealed that nanotubes promote the formation of lamellar crystals with average thickness of 20 nm at different cooling rates. These structural and morphological changes play an important role on the electrical properties of nanocomposites. It was found that higher concentration of nanotubes and crystallinity promotes electrical conductivity of nanocomposites in the order of semiconductors (until 1 × 10?4 S cm?1) as well as permittivity of 20 at different tested frequencies. This may due to the interconnected networks of nanotubes throughout the crystalline structure formed in PEN nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41765.  相似文献   

15.
Poly(lactic acid)/poly(?‐caprolactone)/carbon nanotube (PLA/PCL/CNT) nanocomposites (NCs) were melt‐processed in a conventional industrial‐like twin‐screw extruder maintaining a constant PLA/PCL 80/20 wt. ratio. CNTs located in the thermodynamically favored PCL phase and, as a result, the “sea–island” morphology of the unfilled blend was replaced by a more continuous PCL dispersed phase in the ternary NCs. Rheological and electrical percolation took place at the same CNT contents (over 1.2 wt %) that TEM images suggest continuity of the PCL phase. The electrical and the low‐strain mechanical behaviors upon CNT addition were similar in the reference binary PLA/CNT and ternary PLA/PCL/CNT NCs. In the percolated NCs, the conductivity became 106–107 times higher than in the insulating compositions, while the Young modulus increased linearly upon the addition of CNT (12% increase at 4.9 wt % loading). Moreover, all the PLA/PCL/CNT NCs showed a ductile behavior (elongation at break >130%) similar to that of the unfilled PLA/PCL blend (140%), in contrast to the brittle behavior of binary PLA/CNT NCs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45265.  相似文献   

16.
Thermally conductive polystyrene (PS)/multi‐walled carbon nanotubes (MWNTs) nanocomposites was prepared through a simple solution‐evaporation method assisted by ultrasonic irradiation. To enhance the dispersion of MWNTs in PS, MWNTs were chemically functionalized with poly(styrene‐co‐maleic anhydride) (SMA) (MWNT‐g‐SMA), which had benzene group and exhibited strong affinity with PS. The thermal conductive properties of PS increased and the mechanical properties decreased in presence of MWNTs, while by addition of MWNT‐g‐SMA, the properties of the composites can be improved to some extent. The thermal conductivity can reach 0.89 W/m K for the composite with 33.3 vol % MWNT‐g‐SMA, which was four times higher than that of neat PS. A linear increase of the thermal conductivity was observed with increasing MWNTs‐g‐SMA content, and the Maxwell–Eucken model and the Agari model were used for theoretical evaluation. Compared with MWNT‐OH, MWNT‐g‐SMA with larger diameter exhibited diffused boundary with the PS matrix, resulting from the strong interfacial bonding of the two phases. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

17.
A new and effective route to synthesize conducting polyaniline‐multiwalled carbon nanotube (PANI ‐f‐MWNT) nanocomposites (where ‘f’ denotes that the MWNTs have been functionalized) starting with amine‐protected 4‐aminophenol is reported. Aminophenol‐functionalized MWNTs were initially synthesized by functionalizing acyl chloride‐terminated nanotubes with N‐(tert‐butoxycarbonyl)‐4‐aminophenol followed by the in situ chemical oxidative grafting of aniline in the presence of ammonium persulfate as an oxidizing agent. Control of the morphology and thickness of the polymer–MWNT nanocomposites was achieved by varying the weight ratios of aniline monomers and MWNTs in the polymerization process. Fourier transform infrared spectroscopy was employed to characterize the initial changes in surface functionalities which also confirmed that PANI was covalently grafted to the MWNTs. Electron microscopy and UV‐visible absorption spectroscopy were employed to characterize the morphology and chemical structure of the resulting hybrids. The results obtained indicate that the structure of the MWNTs was not perturbed by the incorporation of PANI. The content of the polymer in the nanocomposites was determined thermogravimetrically, while the electrical conductivity was obtained using four‐probe measurements. The PANI ‐f‐MWNT nanocomposites were adopted as templates for further decoration with gold nanoparticles in solution, thus opening new possibilities for their prospective technological applications. Copyright © 2010 Society of Chemical Industry  相似文献   

18.
Conventional dry‐jet wet fiber spinning techniques were used to fabricate continuous PAN/MWNT composite fibers with up to 20 wt.‐% nanotube loading. PAN at the MWNT interface exhibited lower solubility under thermodynamically favorable conditions than in bulk PAN, indicating good interfacial interaction. Due to the PAN/MWNT interaction at the interface, thermal shrinkage decreases with increasing MWNT loading (5 to 20 wt.‐%). For high MWNT loadings, PAN/MWNT composite fiber at 15 wt.‐% MWNT loading showed an axial electrical conductivity of 1.24 S · m?1. For all loadings, PAN/MWNT composite fibers exhibited higher tensile moduli than theoretically predicted by rule‐of‐mixture calculations, suggesting good reinforcement of the PAN by MWNT.

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19.
In this article is reported the preparation of carbon nanohorn (CNH)/graphene nanoplates (GNP)/polystyrene (PS) nanocomposites through in‐situ bulk polymerization of styrene monomer in the presence of CNH, followed by the addition of suspension polymerized GNP/PS bead during polymerization of styrene, as next‐generation multifunctional material for high electrical conductivity and electromagnetic interference shielding effectiveness (EMI SE) applications. Morphological analysis revealed selective dispersion of CNH in bulk polymerized PS matrix, where GNP/PS beads were randomly distributed. The formation of continuous CNH–CNH conductive path and GNP–CNH–GNP or CNH–GNP–CNH conductive network throughout the PS matrix at exceptionally low loading of CNH (1.0 wt %) and GNP (0.15 wt %) leads to high electrical conductivity (6.24 × 10?2 S cm?1) and EMI SE ~(?24.83 dB) when the nanocomposites was prepared in the presence of 75 wt % GNP/PS bead. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42803.  相似文献   

20.
Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and unfunctionalized MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced the aromatic amine (COC6H4-NH2) groups on the side wall. The F-MWNTs were chemically bonded with the PCL chains in the F-MWNT/PCL, as indicated by the appearance of the amide II group in the FT-IR spectrum. The TGA thermograms showed that the F-MWNT/PCL had better thermal stability than PCL and P-MWNT/PCL. The PCL and the nanocomposite nanofibers were prepared by an electrospinning technique. The nanocomposites that contain more than 2 wt% of MWNTs were not able to be electrospun. The bead of the F-MWNT/PCL nanofiber was formed less than that of the P-MWNT/PCL. The nanocomposite nanofibers showed a relatively broader diameter than the pure PCL nanofibers. The MWNTs were embedded within the nanofibers and were well oriented along the axes of the electrospun nanofibers, as confirmed by transmission electron microscopy.  相似文献   

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