Amino‐functionalized multiple‐walled carbon nanotubes‐polyimide nanocomposite films fabricated by in situ polymerization

For the preparation of high‐quality polymeric carbon nanocomposites, it is required that carbon nanotubes are fully compatible with matrix polymers. For this purpose, amino‐functionalized multiple‐walled carbon nanotubes (a‐MWNTs) were synthesized. The a‐MWNTs/polyimide nanocomposite films were prepared through in situ polymerization. According to the spectroscopic characterizations, the a‐MWNTs were homogeneously dispersed in the nanocomposite films as the acid‐functionalized MWNTs. The mechanical properties of the polyimide composite were also studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Carbon nanotube reinforced rigid‐rod polyimide

Multiwalled carbon nanotube/rigid‐rod polyimide composite films have been prepared by casting a solution of precursor polymer (polyamide acid) containing multiwalled carbon nanotubes (MWNTs) into thin films, followed by a thermal imidization treatment. The composite films were characterized by FTIR, TEM, DSC, TGA and TMA, and the film tensile properties were also examined. The presence of 1.0% MWNTs in the polymer matrix led to more than twofold increase in tensile strength of the rigid‐rod polyimide composite films and improved thermal stability, but reduced in thermal deformation. However, the tensile property did not show further increase when the film contained higher composition of MWNTs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Efficient dispersion of multi‐walled carbon nanotubes by in situ polymerization

Multi‐walled carbon nanotube (MWNT)‐reinforced polyimide nanocomposites were synthesized by in situ polymerization of monomers in the presence of acylated MWNTs. The acyl groups associated with the MWNTs participated in the reaction through the formation of amide bonds. This process enabled uniform dispersion of MWNT bundles in the polymer matrix. The resultant MWNT–polyimide nanocomposite films were optically transparent with significant mechanical enhancement at a very low loading (0.5 wt%). Evidence has been obtained for improved interactions between the nanotubes and the matrix polymer. Copyright © 2006 Society of Chemical Industry     

Preparation and properties of novel epoxy composites containing electrospun PA6/F‐MWNTs fibers

The Nylon 6 (PA6)/the functionalized multiwalled carbon nanotubes (F‐MWNTs) fibrous membranes were fabricated by electrospinning, and then incorporated into an epoxy matrix. Their morphology, thermal stability, mechanical properties, thermal conductivities, and electrical resistivity were investigated. The electrospun PA6/F‐MWNTs fibers performed as a skeleton in the epoxy matrix, and the well interfacial adhesion between the epoxy matrix and the PA6/F‐MWNTs fibers leads to high mechanical properties of composites. The PA6 serves as an intermediate layer and alleviates the modulus mismatch between the stiff MWNTs and the soft epoxy matrix. The thermal conductivities of the epoxy composites increase by 27.3, 35.0, and 36.1%, respectively, with 0.5, 1 and 1.5 wt% F‐MWNTs loading in the PA6/F‐MWNTs fibers. At the same time, the PA6 simultaneously retains the high electrical resistivity of these epoxy composites. POLYM. ENG. SCI., 56:1259–1266, 2016. © 2016 Society of Plastics Engineers     

Properties of ultrahigh‐molecular‐weight polyethylene nanocomposite films containing different functionalized multiwalled carbon nanotubes

We compared the thermomechanical properties, morphologies, gas permeabilities, and electrical conductivities of ultrahigh‐molecular‐weight polyethylene (UHMWPE) nanocomposite films containing two types of functionalized multiwalled carbon nanotubes (functionalized MWNTs). Both 2‐hydroxyethyl triphenyl phosphonium‐MWNT (Ph3P‐MWNT) and 1,1,1,3,3,3‐hexafluoro‐2‐phenyl‐2‐propanol‐MWNT (CF3‐MWNT) were used as reinforcing fillers in the fabrication of UHMWPE hybrid films. UHMWPE nanocomposites with various functionalized MWNT contents were solution‐cast to produce the films. The thermomechanical properties and morphologies of the UHMWPE hybrid films were then characterized using differential scanning calorimetry, thermogravimetric analysis, electron microscopy, and mechanical tensile analysis. Transmission electron microscopy studies showed that some of the MWNT particles were dispersed homogeneously within the polymer matrix (on the nanoscale), whereas others were agglomerated. We also found that the addition of only a small amount of functionalized MWNTs was sufficient to improve the thermomechanical properties and the gas barrier of the UHMWPE hybrid films. Even, those hybrid films with low functionalized MWNT contents (i.e., <1 wt%) were found to exhibit much better thermomechanical properties than the pure UHMWPE films. On the other hand, the values of the electrical conductivity remained constant, regardless of the amount of functionalized MWNTs. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Preparation and characterization of alkylated carbon nanotube/polyimide nanocomposites

BACKGROUND: The development of carbon nanotube‐reinforced composites has been impeded by the difficult dispersion of the nanotubes in polymers and the weak interaction between the nanofiller and matrices. Efficient dispersion of carbon nanotubes is essential for the formation of a functional nanotube network in a composite matrix. RESULTS: Multiwalled carbon nanotubes (MWNTs) were incorporated into a polyimide matrix to produce MWNT/polyimide nanocomposites. To disperse well the MWNTs in the matrix and thus improve the interfacial adhesion between the nanotubes and the polymer, ‘branches’ were grafted onto the surface of the nanotubes by reacting octadecyl isocyanate with carboxylated MWNTs. The functionalized MWNTs were suspended in a precursor solution, and the dispersion was cast, followed by drying and imidization to obtain MWNT/polyimide nanocomposites. CONCLUSION: The functionalized MWNTs appear as a homogeneous dispersion in the polymer matrix. The thermal stability and the mechanical properties are greatly improved, which is attributed to the strong interactions between the functionalized MWNTs and the polyimide matrix. Copyright © 2009 Society of Chemical Industry     

Preparation and properties of nadic‐end‐capped cyclotriphosphazene‐containing polyimide/carbon fiber composites

New novel fire‐resistant and heat‐resistant cyclotriphosphazene‐containing polyimide resins were prepared in situ by the polymerization of (p‐aminophenoxy)(phenoxy)cyclotriphosphazenes with 3,3′,4,4′‐benzophenonetetracarboxylic acid or 3,3′,4,4′‐diphenylsulfonetetracarboxylic acid and a crosslink agent, 5‐norbornene‐2,3‐dicarboxylic acid and were used as polymer matrix compositing with a woven carbon fiber to prepare nadic‐end‐capped cyclotriphosphazene‐containing polyimide/carbon fiber composites. The thermal stability, flame retardance, morphology of the surface fracture, and some physical properties of the composites were investigated by thermogravimetric analysis, scanning electron microscopy, and a material testing system, respectively. The composites had good thermal stability, flame retardance, and mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 810–818, 2003     

Swelling,pH sensitivity,and mechanical properties of poly(acrylamide‐co‐sodium methacrylate) nanocomposite hydrogels impregnated with carboxyl‐functionalized carbon nanotubes

A series of novel nanocomposite hydrogels were prepared by a cross‐linking copolymerization method. Structural and morphological characterizations of the nanocomposite hydrogels revealed that a good compatibility exists between poly(acrylamide‐co‐sodium methacrylate) [P(AM‐co‐SMA)] and carboxyl‐functionalized carbon nanotubes (MWNTs–COOH). The P(AM‐co‐SMA)/MWNTs–COOH nanocomposite hydrogels with a suitable MWNTs–COOH loading exhibited better swelling capability, higher pH sensitivity, good reversibility, and repeatability, and rapid response to external pH stimuli, compared with the P(AM‐co‐SMA). The compression mechanical tests revealed that the nanocomposite hydrogel displayed excellent compressive strengths and elastic mechanical properties, with higher ultimate compressive stress, and meanwhile still retain a good recoverable strain in the presence of MWNTs–COOH. These excellent properties may primarily be attributed to effectively dispersing of a suitable MWNTs–COOH loading into the matrix of the polymers and formation of additional hydrogen bonds. The nanocomposite hydrogels were expected to find applications in drug controlled release and issue engineering. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Dispersion of multi‐walled carbon nanotubes in poly(aryl ether ketone) obtained by in situ polymerization

BACKGROUND: Recently, much work has focused on the efficient dispersion of carbon nanotubes (CNTs) throughout a polymer matrix for mechanical and/or electrical matrices. However, CNTs used as enhancement inclusions in a high‐performance polymer matrix, especially in poly(aryl ether ketone) (PAEK), have rarely been reported. Therefore, multi‐walled carbon nanotube (MWNT)‐modified PAEK nanocomposites were synthesized by in situ polymerization of monomers of interest in the presence of pre‐treated MWNTs. RESULTS: This process enabled a uniform dispersion of MWNT bundles in the polymer matrix. The resultant MWNT/PAEK nanocomposite films were optically transparent with significant mechanical enhancement at a very low MWNT loading (0.5 wt%). CONCLUSION: These MWNT/polymer nanocomposites are potentially useful in a variety of aerospace and terrestrial applications, due to the combination of excellent properties of MWNTs with PAEK. Copyright © 2009 Society of Chemical Industry     

Comparative study of silicon‐containing polyimides from different oxydianilines

Silicon‐containing polyimides were synthesized by solution polycondensation of bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride with 3,4‐oxydianiline and 4,4′‐oxydianiline, respectively. All the poly(amic acid) films could be obtained by solution‐casting from N,N‐dimethylacetamide solutions and thermally converted into transparent and tough polyimide films. The physical properties of thin films of those polyimides were compared by DSC, TGA, UV–visible spectroscopy, and dynamic mechanical analysis. The polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 3,4‐oxydianiline exhibited superior energy‐damping characteristic, mechanical properties, and optical transparency, whereas that from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 4,4′‐oxydianiline possessed higher glass‐transition temperature and thermal stability. Because of the unsymmetric structure of the polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 3,4‐oxydianiline, its increasing rate of linear coefficient of thermal expansion with temperature was quicker than that of the polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 4,4′‐oxydianiline. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2363–2367, 2004     

The morphology and thermal properties of multi‐walled carbon nanotube and poly(hydroxybutyrate‐co‐hydroxyvalerate) composite

Nanocomposites based on poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) and multi‐walled carbon nanotubes (MWNTs) were prepared by solution processing. Ultrasonic energy was used to uniformly disperse MWNTs in solutions and to incorporate them into composites. Microscopic observation reveals that polymer‐coated MWNTs dispersed homogenously in the PHBV matrix. The thermal properties and the crystallization behavior of the composites were characterized by thermogravimetric analysis, differential scanning calorimetry and wide‐angle X‐ray diffraction, the nucleant effect of MWNTs on the crystallization of PHBV was confirmed, and carbon nanotubes were found to enhanced the thermal stability of PHBV in nitrogen. Copyright © 2004 Society of Chemical Industry     

In situ preparation of polyimide/amino‐functionalized carbon nanotube composites and their properties

In order to improve the dispersion of carbon nanotubes (CNTs) in polyimide (PI) matrix and the interfacial interaction between CNTs and PI, 4,4′‐diaminodiphenyl ether (ODA)‐functionalized carbon nanotubes (CNTs‐ODA) were synthesized by oxidation and amidation reactions. The structures and morphologies of CNTs‐ODA were characterized using Fourier transform infrared spectrometer, transmission electron microscopy, and thermal gravimetric analysis. Then a series of polyimide/amino‐functionalized carbon nanotube (PI/CNT‐ODA) nanocomposites were prepared by in situ polymerization. CNTs‐ODA were homogeneously dispersed in PI matrix. The influence of CNT‐ODA content on mechanical properties of PI/CNT‐ODA nanocomposites was investigated. It was found that the mechanical properties of nanocomposites were enhanced with the increase in CNT‐ODA loading. When the content of CNTs‐ODA was 3 wt%, the tensile strength of PI/CNT‐ODA nanocomposites was up to 169.07 MPa (87.11% higher than that of neat PI). The modulus of PI/CNTs‐ODA was increased by 62.64%, while elongation at break was increased by 66.05%. The improvement of the mechanical properties of PI/CNT‐ODA nanocomposites were due to the strong chemical bond and interfacial interaction between CNTs‐ODA and PI matrix. POLYM. COMPOS., 35:1952–1959, 2014. © 2014 Society of Plastics Engineers     

Thermal properties of phosphorylated nanodiamond reinforced polyimides

Recently, the preparation of nanodiamond–polymer composites has attracted the attention of materials scientists due to the unique properties of nanodiamonds. In this study, novel polyimide (PI)/phosphorylated nanodiamonds (PNDs) composites were prepared. PNDs were achieved from the reaction of methylphosphonic dichloride with nanodiamonds in dichloromethane. Precursor of polyimide, which is the poly(amic acid) (PAA), was successfully synthesized with 3,3′, 4,4′‐benzophenonetetracarboxylic dianhydride and 4,4′‐oxydianiline in the solution of N,N‐dimethylformamide. Different ratios of phosphorylated nanodiamond particles were added into PAA solution and four different nanocomposite films were prepared. The amount of PNDs in the composite films was varied from 0 wt% to 3 wt%. The structure, thermal and surface properties of polyimide films were characterized by scanning electron microscopy (SEM), ATR‐FTIR, thermogravimetric analysis (TGA), ultraviolet visible spectroscopy, and contact angle. SEM and FTIR results showed that the phosphorylated nanodiamond and PI/PNDs films were successfully prepared. Phosphorylated nanodiamonds were homogeneously dispersed in the polymer matrix and they displayed good compatibility. TGA results showed that the thermo‐oxidative stability of PI/PNDs films was increased with the increasing amount of phosphorylated nanodiamond. POLYM. COMPOS., 37:2285–2292, 2016. © 2015 Society of Plastics Engineers     

Synthesis and properties of homogeneously dispersed polyamide 6/MWNTs nanocomposites via simultaneous in situ anionic ring‐opening polymerization and compatibilization

Toluene 2, 4‐diisocyanate (TDI) functionalized multiwalled carbon nanotubes (MWNTs‐NCO) were used to prepare monomer casting polyamide 6 (MCPA6)/MWNTs nanocomposites via in situ anionic ring‐opening polymerization (AROP). Isocyanate groups of MWNTs‐NCO could serve as AROP activators of ?‐caprolactam (CL) in the in situ polymerization. Fourier transform infrared (FTIR) showed that a graft copolymer of PA6 and MWNTs was formed in the in situ polymerization. MWNTs‐PA6 covalent bonds of the graft copolymer constituted a strong type of interfacial interaction in the nanocomposites and increased the compatibility of MWNTs and MCPA6 matrix. The nanocomposites were characterized for the morphology, mechanical, crystallization, and thermal properties through field emission transmission electron microscopy (FETEM), tensile testing, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). FETEM analysis showed that MWNTs were homogeneously dispersed in MCPA6 matrix. The initial tensile strengths and tensile modulus of the nanocomposite with 1.5 wt % loading of MWNTs were enhanced by about 16 and 13%, respectively, compared with the corresponding values for neat MCPA6. DSC analysis indicated that the crystallization temperature of the nanocomposites was increased by 8°C by adding 1.5 wt % MWNTs compared with pure MCPA6. Besides, it was found that the thermal stability of MCPA6 was improved by the addition of the MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrical conductivity and thermal properties of acrylonitrile‐butadiene‐styrene filled with multiwall carbon nanotubes

Composites of Acrylonitrile‐butadiene‐styrene (ABS) and multiwall carbon nanotubes (MWNTs) have been prepared via solution‐blending. The electrical conductivity of these composites is analyzed. The MWNT‐filled ABS shows percolation point of the electrical conductivity at low filler loadings (1–2 wt%). The micro‐structure of the composites is also analyzed by scanning electron microscopy showing that the nanotubes are dispersed quite homogeneously in the polymer‐matrix. The thermogravimetric analysis is used to study the thermal degradation of ABS/MWNTs composites in nitrogen. MWNTs tend to destabilize the ABS matrix in the 220–450°C degradation regions but improve the thermal stability in the 425–850°C regions. With further addition of MWNTs, the features of the destabilization in the 220–450°C degradation region did not change much but in the 425–850°C degradation process, the MWNTs reinforced stabilization and the quality of the char residue of amorphous carbon deposition was improved. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Synthesis and properties of BCDA‐based polyimide–clay nanocomposites

Bicyclo[2.2.2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BCDA)‐based polyimide–clay nanocomposites were prepared from their precursor, namely polyamic acid, by a solution‐casting method. The organoclay was prepared by treating sodium montmorillonite (Kunipia F) clay with dodecyltrimethylammonium bromide at 80 °C. Polyamic acid solutions containing various weight percentages of organoclay were prepared from 4,4′‐(4,4′‐isopropylidenediphenyl‐1,1′‐diyldioxy)‐dianiline and BCDA in N‐methyl‐2‐pyrrolidone containing dispersed particles of organoclay at 20 °C. These solutions were cast on a glass plate using a Doctor's blade and then heated subsequently to obtain nanocomposite films. The nanocomposites were characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal mechanical analysis, dynamic mechanical analysis, polarizing microscopy, scanning electron microscopy, transmission electron microscopy, wide‐angle X‐ray diffraction (WAXD) and thermogravimetric analysis. The glass transition temperature of the nanocomposites was found to be higher than that of pristine polymer. The coefficient of thermal expansion of the nanocomposites decreased with increasing organoclay content. WAXD studies indicated that the extent of silicate layer separation in the nanocomposite films depended upon the organoclay content. Tensile strength and modulus of the nanocomposite containing 1% organoclay were significantly higher when compared to pristine polymer and other nanocomposites. The thermal stability of the nanocomposites was found to be higher than that of pristine polymer in air and nitrogen atmosphere. Copyright © 2007 Society of Chemical Industry     

Electro conductivities of well‐dispersed PMMA‐g‐MWNTs/6FDA‐based polyimide composites: Effect of chemical structure

PMMA (polymethylmethacrylate), which is miscible with hexafluoropropane dianhydride (6FDA)‐based polyimide, was grafted onto MWNTs surfaces to enhance their dispersion relative to that of pristine MWNTs. The electrical conductivity of the 6FDA‐based composite revealed percolation threshold behavior, and the 6FDA‐4,4′‐(hexafluoroisopropylidene)diamine, (6FpDA):3,5‐diaminobenzoic acid (DABA)/PMMA‐g‐MWNT composite showed a higher percolation threshold concentration and a slightly lower critical exponent compared with those of the 6FDA‐6FpDA composite. Because of the weak interaction energies between 6FDA‐6FpDA:DABA and PMMA, agglomerated domains were formed. Also, the weak interaction energies of the 6FDA‐6FpDA:DABA led to a larger reduction in the normalized transmittance compared with that seen in the 6FDA‐6FpDA composite. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Mechanical,thermal and electrical properties of multi‐walled carbon nanotube/aluminium nitride/polyetherimide nanocomposites

A series of polyimide‐based nanocomposites containing polyimide‐grafted multi‐walled carbon nanotubes (PI‐g MWCNTs) and silane‐modified ceramic (aluminium nitride (AlN)) were prepared. The mechanical, thermal and electrical properties of hybrid PI‐g MWCNT/AlN/polyetherimide nanocomposites were investigated. After polyimide grafting modification, the PI‐g MWCNTs showed good dispersion and wettability in the polyetherimide matrix and imparted excellent mechanical, electrical and thermal properties. The utilization of the hybrid filler was found to be effective in increasing the thermal conductivity of the composites due to the enhanced connectivity due to the high‐aspect‐ratio MWCNT filler. The use of spherical AlN filler and PI‐g MWCNT filler resulted in composite materials with enhanced thermal conductivity and low coefficient of thermal expansion. Results indicated that the hybrid PI‐g MWCNT and AlN fillers incorporated into the polyetherimide matrix enhanced significantly the thermal stability, thermal conductivity and mechanical properties of the matrix. Copyright © 2012 Society of Chemical Industry     

Preparation and Characterization of Aminopropylsilatrane Endcapped Polyimide Films

γ-Aminopropylsilatrane (APS)/γ-aminopropyltriethoxysilane (APTES) end capped polyimide films were prepared by thermal imidization method. Polyamic acid (PAA) was prepared by the reaction of 4,4′-oxydianiline (ODA) with 4,4′-oxydipthalicdianhydride (ODPA) using dimethylacetamide (DMAc) as solvent. The end group of prepared PAA was capped by different percentage of APS/APTES. The polyimide films were characterized by different advanced instrumental techniques for chemical/physical properties. APS end capped PI films show better thermal and mechanical properties and air permeability than APTES end capped polyimide films.     

Incorporation of 4‐aminobenzene functionalized multi‐walled carbon nanotubes in polyaniline for application in formic acid electrooxidation

Incorporation of carbon nanotubes (CNTs) in conducting polymer can lead to new composites with enhanced electrical and mechanical properties. However, the development of such composites has been hampered by the inability to disperse CNTs in polymer matrix due to the lack of chemical compatibility between polymers and CNTs. Covalent sidewall functionalization of carbon nanotube provides a feasible route to incorporate carbon nanotube in polymer. In this work, 4‐aminobenzene groups were grafted onto the surface of multi‐walled carbon nanotube (MWNT) via C? C covalent bond. Polyaniline (PANI)/MWNT composites were fabricated by electrochemical polymerization of aniline containing well‐dissolved functionalized MWNTs. The obtained composites can be used as catalyst supports for electrooxidation of formic acid. Cyclic voltammogram results show that platinum particles deposited in PANI/MWNT composite films exhibit higher electrocatalytic activity and better long‐term stability towards formic acid oxidation than that deposited in pure PANI films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010