Physical properties of phenol-anchored multiwall carbon nanotube/epoxy nanocomposite

Surface functionalization of multiwall carbon nanotubes (MWCNTs) was carried out by introducing a ylide group containing anchored phenol structures. Epoxy nanocomposites filled with modified and pristine carbon nanotubes were prepared, and their mechanical, electrical, and thermal properties were evaluated. Mechanical properties such as tensile strengths and Young’s moduli of the epoxy nanocomposites increased significantly with the addition of the modified MWCNTs compared to the pristine MWCNTs, due to the strong interaction between the modified MWCNTs and the epoxy matrix. Scanning electron microscopy of the fractured epoxy systems revealed that the functionalized MWCNTs were finely dispersed in the matrix, as opposed to the pristine carbon nanotubes. The epoxy/functionalized MWCNT nanocomposite had a lower surface electrical resistance than the epoxy/pristine MWCNT nanocomposite, confirming the effect of functionalization.     

Effects of multi‐walled carbon nanotube functionalization on the morphological and mechanical properties of nanocomposite foams based on poly(vinyl chloride)/(wood flour)/ (multi‐walled carbon nanotubes)

Experimental results are presented for nanocomposite foams based on unplasticized poly(vinyl chloride)/(wood flour)/(multi‐wall carbon nanotubes) (PVC/WF/MWCNTs). The nanocomposite samples were prepared in an internal mixer and foamed via a batch processing method using compression molding. Nanoparticles were functionalized by sodium hypochlorite solution, and the functionalization process was monitored by Fourier‐transform infrared spectroscopy. The effects of MWCNTs (both neat and functionalized) and blowing agent concentration on the morphological properties (cell size and cell density) and mechanical properties (tensile and flexural strength) of the foam samples were studied. The results revealed that foam cell sizes decreased and cell densities increased with addition of MWCNTs. The dispersion of nanoparticles in the PVC medium was increased by functionalization, and the morphological properties of the foams containing functionalized nanoparticles were improved. Density of nanocomposite foams decreased more with functionalized MWCNTs as compared to other samples. Chemical blowing agent concentration had no significant effect on sample density. Mechanical properties of the samples were improved by using functionalized MWCNTs in comparison with those of foams without this component. J. VINYL ADDIT. TECHNOL., 18:161–167, 2012. © 2012 Society of Plastics Engineers     

Properties of PMMA/Carbon nanotubes nanocomposites prepared by “grafting through” method

A number of batch polymerizations were performed to study the effect of multi‐walled carbon nanotubes (MWCNTs) on the properties of PMMA/MWCNTs nanocomposites. To improve the dispersion of nanotubes in PMMA matrix, MWCNTs were functionalized with methacrylate groups via a four‐step modification process and the modified nanoparticles were used to synthesize the nanocomposites. The prepared samples were characterized by Raman spectroscopy, thermogravimetric analysis, dynamic mechanical thermal analysis, differential scanning calorimetry, gel permeation chromatography, UV–visible, and TEM techniques. According to the results, modified nanotubes improved thermal and mechanical properties better than the pristine MWCNTs. The main improvement in the mechanical and thermophysical properties was achieved for the nanocomposite containing 0.5 wt% of MWCNTs. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Poly(methyl methacrylate) nanocomposites based on graphene oxide: a comparative investigation of the effects of surface chemistry on properties and foaming behavior

The effects of oxygen functional groups and alkyl chains at the surface of graphene oxide (GO) on the thermal stability, mechanical properties and foaming behavior of poly(methyl methacrylate) (PMMA) nanocomposites were investigated. Alkyl‐functionalized GO (GO‐ODA) was prepared by grafting octadecylamine (ODA) on the surface of GO. PMMA/GO and PMMA/GO‐ODA nanocomposite were obtained by solution blending and were foamed using supercritical carbon dioxide (scCO₂). GO‐ODA, with the presence of alkyl chains, showed a better dispersion capability in PMMA matrix than GO with a large amount of oxygen functional groups. In addition, the good dispersion capability increased thermal stability and mechanical strength. In comparison with PMMA/GO samples foamed at 70 °C, PMMA/GO‐ODA nanocomposite foams displayed improved cell structures with higher cell density, smaller cell size and more homogeneous cell size distribution, which results from the strong heterogeneous nucleation due to alkyl chains on the GO surface. The foaming behaviors became more complicated at 80 °C as the GO might be intercalated and exfoliated with the aid of scCO₂, thus further enhancing the heterogeneous nucleation during the foaming process. The results indicated that the surface chemistry of GO was closely related to the properties and foaming behavior of the nanocomposites. © 2016 Society of Chemical Industry     

Preparation and characterization of novel polyethylene/carbon nanotubes nanocomposites with core–shell structure

Preparation of novel polyethylene/carbon nanotubes (CNTs) nanocomposites with core–shell structure was presented. The method involved in situ ethylene polymerization in which nanotube surface was treated with Grignard Agent, followed by reacting with active transition metal compound, TiCl₄. The multiwalled carbon nanotubes (MWCNTs) supported catalysts polymerize ethylene to form polymer nanocomposite. MWCNTs were homogeneously dispersed within polymer matrix, and as expected, the resultant nanocomposites featured core–shell structure which was confirmed by HRTEM. For the nanocomposite, the microscopic examination of the cryogenically fractured surface not only ensured a good distribution of carbon nano-particles in the PE matrix but also revealed the ductile-like fracture. The Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed for the study of covalent sidewall functionalization and chemical bonding environment of MWCNTs, also indicated effective immobilization of titanium catalyst on the MWCNTs surface. The crystalline properties, dielectric property and thermal stability of the nanocomposites were determined by WAXD, impedance analyzer and TGA. The dielectric result showed a slight decline of the dielectric constant of the nanocomposites with increase of the polymerization time, and lower dielectric loss was also observed.     

Structure‐property relationship of substituted pyrrolidine functionalized CNT epoxy nanocomposite

Carbon nanotubes (CNTs) based polymer nanocomposites hold the promise of delivering exceptional mechanical properties and multifunctional characteristics. However, the realization of exceptional properties of CNT based nanocomposites is dependent on CNT dispersion and CNT‐matrix adhesion. To this end, we modified MWCNTs by Prato reaction to yield aromatic (phenyl and 2‐hydroxy‐4‐methoxyphenyl) substituted pyrrolidine functionalized CNTs (fCNT1 and fCNT2) and aliphatic (2‐ethylbutyl and n‐octyl) substituted pyrrolidine functionalized CNTs (fCNT3 and fCNT4). The functionalization of CNTs was established by Thermogravimetric analysis (TGA), Raman Spectroscopy, and XPS techniques. Optical micrographs of fCNT epoxy mixture showed smaller aggregates compared to pristine CNT epoxy mixture. A comparison of the tensile results and onset decomposition temperature of fCNT/epoxy nanocomposite showed that aliphatic substituted pyrrolidine fCNT epoxy nanocomposites have higher onset decomposition temperature and higher tensile toughness than aromatic substituted pyrrolidine fCNT epoxy nanocomposites, which is consistent with the dispersion results of fCNTs in the epoxy matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42284.     

The influence of carbon nanotube aspect ratio on the foam morphology of MWNT/PMMA nanocomposite foams

Polymer nanocomposite foams, products from the foaming of polymer nanocomposites, have received increasing attention in both the scientific and industrial communities. Nanocomposite foams filled with carbon nanofibers or carbon nanotubes with high electrical conductivity, enhanced mechanical properties, and low density are potential effective electromagnetic interference (EMI) shielding materials. The EMI shielding efficiency depends on the electrical conductivity and bubble density, which in turn, depend on the properties of the filler. In the current study, multi walled carbon nanotubes (MWNT) with controlled aspect ratio were used to alter the bubble density in MWNT/poly(methyl methacrylate) (PMMA) nanocomposites. It was found that the nanocomposite foams filled with shorter MWNT had higher bubble density under the same foaming conditions and MWNT concentration. Both the ends and sidewalls of carbon nanotubes can act as heterogeneous bubble nucleation sites, but the ends are more effective compared to the sidewalls. Shorter nanotubes provide more ends at constant MWNT concentration compared to long nanotubes. As a result, the difference in the foam morphology, particularly the bubble density, is due to the difference in the number of effective bubble nucleation sites.     

Crystallization and mechanical behavior of covalent functionalized carbon nanotube/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) nanocomposites

To improve the dispersity of multi‐walled carbon nanotubes (MWCNTs) in poly(3‐hydroxybutyrate‐co?3‐hydroxyvalerate) (PHBV) matrix, MWCNTs functionalized with carboxyl groups, hydroxyl groups, and atactic poly (3‐hydroxybutyrate) (ataPHB) through acid oxidation, esterification reaction, and “grafting from” method, respectively, were used to fabricate nanofiller/PHBV nanocomposites. The crystallization behavior, dispersion of MWCNTs before and after functionalization in PHBV matrices, and mechanical properties of a series of nanocomposites were investigated. The differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscope results suggested that the four types of MWCNTs acted as effective heterogeneous nucleation agents, inducing an increase in the crystallization rate, crystallinity, and crystallite size. Scanning electron microscope observations demonstrated that functionalized MWCNTs showed improved dispersion comparing with MWCNTs, suggesting an enhanced interfacial interaction between PHBV and functionalized MWCNTs. Consequently, the mechanical properties of the functionalized MWCNTs/PHBV nanocomposites have been improved as evident from dynamic mechanical and static tensile tests. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42136.     

Crystallinity of biodegradable polymers reinforced with functionalized carbon nanotubes

Well-dispersed multiwall carbon nanotubes (MWCNTs) were prepared by grafting poly(L-lactide-co-ε-caprolactone) (PLACL) biodegradable copolymer onto the sidewall of hydroxylated MWCNTs using oligomeric L-lactide (LA) and ε-caprolactone (CL). After preparation of MWCNT/PLACL composites, the effect of functionalized MWCNTs on crystallinity of PLACL was investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and polarized light optical microscopy (POM). The surface functionalization effectively improved the dispersion and adhesion of MWCNTs which acted as reinforcing filler in the PLACL polymer matrix and hence improved the physical and thermomechanical properties of the nanocomposites. The glass transition temperature (T _g) and the crystallinity of nanocomposites decreased in comparison with those of neat PLACL when the concentration of functionalized MWCNTs in nanocomposites was 0.5 wt%. With further increment in concentration of functionalized MWCNTs, the T _g of composites increased until the T _g of neat PLACL, and also the crystallinity of composites increased. The functionalized MWCNTs have no significant effect on the melting point of nanocomposites. The MWCNTs acted as heterogeneous nucleation points and increased the lamella size and therefore the crystallinity of PLACL. Furthermore, the larger agglomerated clusters of both kinds of MWCNTs (i.e., MWCNT-grafted-PLACL and pristine MWCNTs) are more effective than small clusters as nucleation points for growing the spherulites.     

A facile route to develop electrical conductivity with minimum possible multi‐wall carbon nanotube (MWCNT) loading in poly(methyl methacrylate)/MWCNT nanocomposites

Today, we stand at the threshold of exploring carbon nanotube (CNT) based conducting polymer nanocomposites as a new paradigm for the next generation multifunctional materials. However, irrespective of the reported methods of composite preparation, the use of CNTs in most polymer matrices to date has been limited by challenges in processing and insufficient dispersability of CNTs without chemical functionalization. Thus, development of an industrially feasible process for preparation of polymer/CNT conducting nanocomposites at very low CNT loading is essential prior to the commercialization of polymer/CNT nanocomposites. Here, we demonstrate a process technology that involves in situ bulk polymerization of methyl methacrylate monomer in the presence of multi‐wall carbon nanotubes (MWCNTs) and commercial poly(methyl methacrylate) (PMMA) beads, for the preparation of PMMA/MWCNT conducting nanocomposites with significantly lower (0.12 wt% MWCNT) percolation threshold than ever reported with unmodified commercial CNTs of similar qualities. Thus, a conductivity of 4.71 × 10^?5 and 2.04 × 10^?3 S cm^?1 was achieved in the PMMA/MWCNT nanocomposites through a homogeneous dispersion of 0.2 and 0.4 wt% CNT, respectively, selectively in the in situ polymerized PMMA region by using 70 wt% PMMA beads during the polymerization. At a constant CNT loading, the conductivity of the composites was increased with increasing weight percentage of PMMA beads, indicating the formation of a more continuous network structure of the CNTs in the PMMA matrix. Scanning and transmission electron microscopy studies revealed the dispersion of MWCNTs selectively in the in situ polymerized PMMA phase of the nanocomposites. Copyright © 2012 Society of Chemical Industry     

Radiation resistant metal decorated MWCNTs/PMMA nanocomposite films with enhanced thermomechanical properties

UV/O₃ radiation and chemical resistant nanocomposite films of functionalized/metal decorated multiwall carbon nanotubes (MWCNTs) with polymethylmethacrylate (PMMA) are synthesized. Silver nanoparticles are decorated on the surface of UV/O₃ functionalized MWCNTs by both reduction and in situ growth from AgNO₃ aqueous solution. Microscopic studies reflect the better dispersion of UV/O₃ functionalized/silver decorated MWCNTs in polymer matrix contributing in enhancement of thermal stability, thermomechanical strength, glass transition temperatures, and thermal conductivity of nanocomposites even at 0.25 wt% MWCNTs additions. The thermal stability of nanocomposite film (0.25 wt% loading), prepared by using a surfactant (Sodium dodecyl sulfate) is increased to about 27°C while the thermomechanical properties are raised up to 76% at 100°C. Thermal and thermomechanical behavior of pre‐ and post‐UV/O₃ irradiated nanocomposite films are compared with neat polymer. The results reveal that UV/O₃ functionalized MWCNTs can effectively disperse the radiation and have a dramatic reinforcement effect on the nature of the degradation of PMMA matrix. POLYM. COMPOS., 36:969–978, 2014. © 2014 Society of Plastics Engineers     

Electrical and rheological properties of MWCNT/polycarbonate nanocomposites

The electrical and rheological percolation behaviors of polycarbonate/multiwall carbon nanotube nanocomposites were investigated. To determine the effects of surface functionalization on a carbon nanotube surface, poly(styrene-co-acrylonitrile) (SAN)-grafted multiwall carbon nanotubes were prepared using surface-initiated atom transfer radical polymerization. The amount of grafted SAN was controlled by changing the polymerization time and was characterized using TGA. FT-IR and TEM were used to characterize the surface of the functionalized carbon nanotubes. The rheological and electrical percolation behaviors of the SAN-grafted multiwall carbon nanotube/polycarbonate nanocomposites were compared to those of pristine multiwall carbon nanotubes, where the effects were shown to increase with increasing SAN content. The results are attributed to the compatibility of SAN with polycarbonates, which induced uniform dispersion of the functionalized carbon nanotubes. Uniform dispersion was also confirmed by evaluating a tensile-fractured nanocomposite specimen.     

Mild functionalization of carbon nanotubes filled epoxy composites: Effect on electromagnetic interferences shielding effectiveness

The effect of nitric acid mild functionalized multiwalled carbon nanotubes (MWCNTs) on electromagnetic interference (EMI) shielding effectiveness (SE) of epoxy composites was examined. MWCNTs were oxidized by concentrated nitric acid under reflux conditions, with different reaction times. The dispersion of MWCNTs after functionalization was improved due to the presence of oxygen functional groups on the nanotubes surface. Functionalization at 2 h exhibits the highest EMI SE and electrical conductivity of MWCNTs filled epoxy composites. However, EMI shielding performance of MWCNTs filled epoxy composite declined when the functionalization reaction time was prolonged. This was due to extensive damage on the MWCNT structure, as verified by a Raman spectroscope. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42557.     

Thermal‐Insulation,Electrical, and Mechanical Properties of Highly‐Expanded PMMA/MWCNT Nanocomposite Foams Fabricated by Supercritical CO2 Foaming

Foaming behavior of poly(methyl methacrylate) (PMMA)/multi‐walled carbon nanotubes (MWCNTs) nanocomposites and thermally‐insulating, electrical, and mechanical properties of the nanocomposite foams are investigated. PMMA/MWCNT nanocomposites containing various amounts of MWCNTs are first prepared by combining solution and melt blending methods, and then foamed using CO₂. The foaming temperature and MWCNT content are varied for regulating the structure of PMMA/MWCNT nanocomposite foams. The electrical conductivity measurement results show that MWCNTs have little effect on the electrical conductivity of foams with large expansion ratio. Thermal conductivities of both solid and foamed PMMA/MWCNT nanocomposites are measured to evaluate their thermally insulating properties. The gas conduction, solid conduction, and thermal radiation of the foams are calculated for clarifying the effects of cellular structure and MWCNT content on thermal insulation properties. The result demonstrates that MWCNTs endowed foams with enhanced thermal insulation performance by blocking thermal radiation. Moreover, the compressive testing shows that MWCNTs improve the compressive strength and rigidity of foams. This research is essential for optimizing environmentally friendly thermal insulation nanocomposite foams with enhanced thermal‐insulation and compressive mechanical properties.     

Improvement in mechanical and thermal properties of phenolic foam reinforced with multiwalled carbon nanotubes

Phenolic foams reinforced with pristine and functionalized multiwalled carbon nanotubes (MWCNTs) were fabricated to develop fire‐resistant materials with improved mechanical properties. The influences of the contents of carboxyl multi‐walled carbon nanotubes (MWCNTs‐COOH) and of MWCNTs types on the compressive properties of the composite foams were investigated. The microstructure and detailed failure behavior of MWCNTs/phenolic composite foams were studied using scanning electron microscopy (SEM) and in situ quasistatic compression inside SEM, respectively. In addition, thermal performances were evaluated by thermogravimetric analysis (TGA) and vertical burning method. It is found that as heterogeneous nucleation agents, MWCNTs increase cell density and decrease cell size of the produced foams, and that as reinforcements located in cell walls, MWCNTs impart high strength and stiffness to brittle foams. Moreover, MWCNTs reinforced foams have higher thermal stability than raw foams and exhibit similar excellent resistance to flame, confirming the effectiveness of MWCNTs as stabilizers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1479–1488, 2013     

Properties and degradation behavior of surface functionalized MWCNT/poly(L‐lactide‐co‐ε‐caprolactone) biodegradable nanocomposites

In this research, poly(L ‐lactide‐co‐ε‐caprolactone) (PLACL) reinforced with well‐dispersed multiwalled carbon nanotubes (MWCNTs) nanocomposites were prepared by oxidization and functionalization of the MWCNT surfaces using oligomeric L ‐lactide (LA) and ε‐caprolactone (CL). It is found that the surface functionalization can effectively improve the dispersion and adhesion of MWCNTs in PLACL. The surface functionalization will have a significant effect on the physical, thermomechanical, and degradation properties of MWCNT/PLACL composites. The tensile modulus, yield stress, tensile strength, and elongation at break of composite increased 49%, 60%, 70%, and 94%, respectively, when the concentration of functionalized MWCNTs in composite is 2 wt %. The in vitro degradation rate of nanocomposites in phosphate buffer solution increased about 100%. The glass transition temperature (T_g) of composites was decreased when the concentration of functionalized MWCNTs is 0.5 wt %. With further increasing the concentration of functionalized MWCNTs, the T_g was increased. The degradation kinetics of nanocomposites can be engineered and functionalized by varying the contents of pristine or functionalized MWCNTs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Silane Modification of Carbon Nanotubes and Preparation of Silane Cross‐Linked LLDPE/MWCNT Nanocomposites

The objective of this study is to investigate the effects of carbon nanotube (CNT) content, surface modification, and silane cross‐linking on mechanical and electrical properties of linear low‐density polyethylene/multiwall CNT nanocomposites. CNTs were functionalized by vinyltriethoxysilane to incorporate the ─O─C2H5 functional groups and were melt‐blended with polyethylene. Silane‐grafted polyethylene was then moisture cross‐linked. Silanization of CNT was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and EDX analysis. Hot‐set test results showed that silane cross‐linking of polyethylene and incorporation of modified CNTs into polyethylene led to an increase in cross‐linking density and the number of entanglements resulting in a decrease in elongation. It was found that the addition of pristine multiwall carbon nanotubes (MWCNTs) and functionalized MWCNTs does not affect silane cross‐linking density. Silane modification resulted in a stronger adhesion of the silane cross‐linked LLDPE to silanized MWCNTs according to scanning electron microscopy micrographs. Additionally, the electrical tests revealed that the silane modification of CNTs results in an improvement in electrical properties of nanocomposites, while silane cross‐linking will not have an effect on electrical properties. Rheological properties of MWCNT/LLDPE nanocomposites have been studied thoroughly and have been discussed in this study. Moreover, according to TGA test results, modification of the MWCNTs led to a better dispersion of them in the LLDPE matrix and consequently resulted in an improvement in thermal properties of the nanocomposites. Crystallinity and melting properties of the nanocomposites have been evaluated in detail using DSC analysis. J. VINYL ADDIT. TECHNOL., 26:113–126, 2020. © 2019 Society of Plastics Engineers     

Viscoelasticity and thermal stability of poly(arylene ether nitrile) nanocomposites with various functionalized carbon nanotubes

Poly(arylene ether nitrile) (PEN) nanocomposites containing various functionalized multi‐walled carbon nanotubes (MWCNTs) were prepared through a solution‐casting method. The as‐prepared PEN nanocomposites were investigated using parallel‐plate rheometry and thermogravimetric analysis, aimed at examining the effect of surface functionalization on the dispersion of MWCNTs from the viscoelastic and thermal properties. The linear viscoelasticy results indicated that 4‐aminophenoxyphthalonitrile‐grafted MWCNTs presented better dispersion in the PEN matrix than purified and carboxylic MWCNTs because the corresponding composite showed the lowest rheological percolation threshold, which was further confirmed from scanning electron microscopy, dissolution experiments and solution rheological experiments. The thermogravimetric analysis results revealed that the presence of 4‐aminophenoxyphthalonitrile‐grafted and carboxylic MWCNTs retarded the depolymerization compared with purified MWCNTs, showing a marked increase in the temperature corresponding to a loss of 5 wt% (increased by 14–22 °C) and maximum rate of decomposition (increased by 4–8 °C). Both the state of dispersion and the surface functionalization of MWCNTs are very important to the thermal stability of the PEN matrix. Copyright © 2011 Society of Chemical Industry     

Effects of three surfactant types of anionic, cationic and non-ionic on tensile properties and fracture surface morphology of epoxy/MWCNT nanocomposites

Three types of surfactants were used to enhance the dispersion of multi-wall carbon nanotubes (MWCNTs) in the epoxy matrix. MWCNTs were separately treated with non-ionic (polyoxyethylene octyl phenyl ether, Triton X-100), cationic (hexadecyl-trimethyl-ammonium bromide, CTAB) and anionic (sodium dodecyl sulfate, SDS) surfactants and their effects were evaluated on the dispersion state and surface chemistry, as well as on the tensile properties and tensile fracture surface morphology of MWCNTs/epoxy nanocomposites. The active surfaces of the carbon nanotubes were characterized by FTIR. The non-ionic surfactant, Triton X-100, had the best effect on dispersion of the MWCNT in the epoxy matrix, thus, positively affecting the tensile parameters of the corresponding nanocomposites which were attributed to the ??bridging?? effects between the MWCNT and epoxy, introduced by the hydrophobic and hydrophilic heads of the corresponding surfactant. Presence of MWCNTs as reinforcing agent increased the elastic modulus of nanocomposites, indicating the improved interfacial adhesion between CNTs and polymer matrix. The regions of nucleation and propagation of cracks were clearly seen in the SEM micrographs of the tensile fracture surface of the nanocomposites. The cracks deviated on reaching the carbon nanotubes. The dispersing aiding capabilities of the three surfactants used in the present study were as follows: cationic?<?anionic?<?non-ionic.     

Achieving β-phase poly(vinylidene fluoride) from melt cooling: Effect of surface functionalized carbon nanotubes

Poly(vinylidene fluoride) (PVDF) based nanocomposites with different surface-functionalized multi-walled carbon nanotubes (MWCNTs) were prepared by melt mixing in a small scale compounder. With the incorporation of commercial functionalized MWCNTs, the β-phase in PVDF can be directly achieved from melt cooling, as verified by results of Fourier transform infrared spectrum and X-ray diffraction. Interestingly, nanocomposites with amino group functionalized MWCNTs showed the highest percentage of β-phase (17.4%) formation in PVDF, followed by those with hydroxyl groups (11.6%) and unmodified MWCNTs (9.4%). However, the nanocomposites containing MWCNTs with carboxyl groups which were thought to be able to well interact with the dipoles on PVDF chains have the lowest amount of β-phase, i.e. 4.7%. The analysis on the mechanism of the influence of surface functionalization of MWCNTs on the formation of β-phase in PVDF shows that the combined effects of the dispersion of MWCNTs and the nanotube–polymer interactions account for the formation of the β-phase in PVDF.