Chouit et al. Nanoscale Research Letters 2014, 9:288 http://www.nanoscalereslett.com/content/9/1/288 NANO EXPRESS Open Access Synthesis and characterization of HDPE/N-MWNT nanocomposite films Fairouz Chouit1*, Ounassa Guellati1,2,3, Skander Boukhezar1, Aicha Harat1, Mohamed Guerioune1 and Nacer Badi4 Abstract In this work, a series of nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) with several weight percentages (0.1, 0.4, 0.8, and 1.0 wt.%) were synthesized by catalytic chemical vapor deposition (CCVD) technique. The N-MWCNTs were first characterized and then dispersed in high-density polyethylene (HDPE) polymer matrix to form a nanocomposite. The HDPE/N-MWCNT nanocomposite films were prepared by melt mixing and hot pressing; a good dispersion in the matrix and a good N-MWCNT-polymer interfacial adhesion have been verified by scanning electron microscopy (SEM). Raman spectroscopy measurements have been performed on prepared samples to confirm the presence and nature of N-MWNTs in HDPE matrix. The X-ray diffraction (XRD) analysis demonstrated that the crystalline structure of HDPE matrix was not affected by the incorporation of the N-MWNTs. Keywords: Nanocomposite; Carbon nanotube; High-density polyethylene; Raman spectroscopy; XRD; SEM Background The carbon nanotubes (CNTs) have attracted a great at- tention in recent years in the field of nanocomposite materials as reinforcing fillers because of their excellent mechanical and thermal properties [1,2]. They possess an extremely high elastic modulus comparable to that of diamond [3,4]. In addition, they exhibit electrical con- ductivity as high as 105 to 107 S/m [5] and can transform an insulating polymer into a conducting composite at a very low loading due to their extremely high aspect ratio. The CNT/polymer nanocomposite is one of the most promising fields for CNT applications, which generally ex- hibits excellent properties that differ substantially from those of pristine polymer matrix. A good dispersion of CNTs in polymer and their strong interfacial adhesion or coupling are the two key issues to ensure success of fabricating CNT/polymer nanocomposite with ex- cellent properties [6,7]. To that end, CNT functionaliza- tion is necessary before compounding with polymers. Three general approaches have been adopted in attempts to modify the surface of CNTs to promote the inter- facial interactions: chemical, electrochemical, and plasma treatments. For example, Velasco-Santos et al. [8] placed * Correspondence: chouit1fairouz@yahoo.fr 1Laboratoire d'Etude et de Recherche des Etats Condensés (LEREC), Département de Physique, Université Badji-Mokhtar, BP. 12, Annaba 23000, Algeria Full list of author information is available at the end of the article © 2014 Chouit et al.; licensee Springer. This is a Attribution License (http://creativecommons.or in any medium, provided the original work is p different organofunctional groups on MWCNTs using an oxidation and silanization process. Bubert et al. [9] modi- fied the surface of CNTs by using low-pressure oxygen plasma treatment. They detected hydroxide, carbonyl, and carboxyl functionality on the surface layers of the CNTs by using X-ray photoelectron spectroscopy (XPS). Polyethylene (PE) is one of the most widely used thermo- plastic. Among all PE types, high-density polyethylene (HDPE) is a commonly used thermoplastic with high degree of crystalline structure along with higher ten- sile strength [10-12]. Due to its low cost and processing energy consumption, HDPE resin is ideal for many appli- cations such as orthopedic implants and distribution pipes [11]. Moreover, HDPE can effectively resist corrosions in- cluding moisture, acids/alkalis, and most of the chemical solvents at room temperature. High-power ultrasonic mixers [13], surfactants, solu- tion mixing [14], and in situ polymerization have been used to produce CNT/polymer composites. These tech- niques appear to be environmentally contentious and may not be commercially viable. The melt mixing technique reported here is a simple and economical approach since the nanofillers are added directly to the polymer melt. However, the challenge in melt mixing is to achieve a good dispersion of the nanofillers through shear forces as well as a strong coupling between nanofillers and the matrix [15]. n Open Access article distributed under the terms of the Creative Commons g/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction roperly credited. mailto:chouit1fairouz@yahoo.fr http://creativecommons.org/licenses/by/2.0 a 20 nm b Figure 1 HR-TEM (a) and SEM (b) micrographs of N-MWNTs. Chouit et al. Nanoscale Research Letters 2014, 9:288 Page 2 of 6 http://www.nanoscalereslett.com/content/9/1/288 It has been shown that CNTs can alter the crystallization kinetics of semi-crystalline polymers [16,17]. Sandler et al. [18] have melt-blended polyamide-12 with MWCNTs and carbon fibers using a twin-screw micro-extruder, and then fibers were produced from the prepared blends. They highlighted that both the intrinsic crystalline quality of the nanocomposite and the orientation of the embedded CNTs are the major factors controlling the reinforcing capability of CNTs. We report in this paper on the preparation of nitrogen- doped multi-walled carbon nanotube (N-MWNT)/high- density polyethylene (HDPE) composites using melt blending. The presence of N-MWNTs in HDPE and 1200 1300 1400 In te ns ity (a , u ,) Wave num Figure 2 Raman spectrum of N-MWNTs. morphology of the composites were investigated using scanning electron microscopy (SEM) and Raman spec- troscopy techniques. The crystallization of the nanocom- posites is subsequently discussed using X-ray diffraction combined with Raman analysis. Methods Materials The main materials used in this study are N-MWNTs (> 97% purity) with an outer mean diameter around 40 nm and a length over 10 μm. These nanotubes were synthesized by catalytic chemical vapor deposition (CCVD) technique using a mixture of C2H6/Ar/NH3 and 20 wt.% iron catalyst 1500 1600 1700 ber (cm-1) 0 200 400 600 800 1000 W ei gh t D er iv (% ° C ) Oxydation Temperature (°C) Figure 3 Derivative of TGA curve of N-MWNTs. Chouit et al. Nanoscale Research Letters 2014, 9:288 Page 3 of 6 http://www.nanoscalereslett.com/content/9/1/288 supported by alumina powder. The polymer matrix used is HDPE with trade name TR144, supplied by Sonatrach Company CP2K (Skikda, Algeria). The melt index of HDPE pellets is 0.30 with a density of 0.942 to 0.947 g/cm3. Nanocomposite preparation N-MWNTs/HDPE were prepared via the melt-compounding method using a twin-screw mixer (Brabender, Duisburg, Germany), the processing temperature was kept at 167°C, and the screw speed amounted to 100 rpm for 10 min. The weight fractions of N-MWNT filler were fixed at Figure 4 SEM micrographs of HDPE/N-MWNT nanocomposite. 0.1, 0.4, 0.8, and 1.0 wt.%. The composite was then hot- pressed at 177°C, under a pressure of 100 bars for 5 min, in order to obtain films using 50 × 70 × 0.5 mm3 mold di- mensions. In addition, a reference sample of bare HDPE was prepared in a very similar way. Characterization techniques The morphology of the N-MWNTs was examined by SEM on a JEOL 6700-FEG microscope (Akishima, Tokyo, Japan). High-magnification transmission electron micros- copy (HRTEM) observations were carried out using a JEOL JEM-2010 F under an accelerated voltage of 200 kV 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 G 1594 D 1340In te ns ity (a .u .) Wave number (cm -1) Figure 5 Raman shift of HDPE/N-MWNT nanocomposite. Chouit et al. Nanoscale Research Letters 2014, 9:288 Page 4 of 6 http://www.nanoscalereslett.com/content/9/1/288 with a point-to-point resolution of 0.23 nm. The thermo- gravimetric analysis (TGA) was performed on a Q5000 apparatus (TA Instruments, New Castle, DE, USA) where the combustion ran in air atmosphere at a flow rate of 20 ml/min, up to 1,000°C at 10°C/min. Raman spectros- copy was carried out on a micro-Raman Renishaw spec- trometer Ramascope 2000 (Gloucestershire, UK), with a spot size of 1 μm2, a resolution of 1 cm−1, and a He-Ne laser beam operating at an excitation wavelength of 632.8 nm. X-ray diffraction measurements have been per- formed by PANalytical system (Almelo, The Netherlands; CuKα as a radiation source with λ = 1.0425 Ǻ, 2θ from 10° to 60°). 10 20 3010 20 3010 20 30 C N T (0 02 ) (0 20 ) (2 10 ) (2 00 ) (1 10 ) 2 The Figure 6 X-ray patterns of HDPE and HDPE/N-MWNTs. Results and discussions Analysis of carbon nanotubes SEM studies give further information on the morph- ology and microstructure of the prepared N-MWNTs. Figure 1 is a typical magnification HRTEM image of the synthesized product showing the bamboo-shaped MWNTs with 97% purity and high selectivity (approxi- mately 12 to 100 nm) with an outer diameter around 40 nm [19,20]. In order to obtain more information regarding the ni- trogen doping and crystallinity of the entire nitrogen- doped MWNTs, Raman spectrum is plotted in Figure 2. It shows two main features: the D and G bands. The first 40 50 6040 50 6040 50 60 C N T (0 04 ) C N T (1 00 ) (0 11 ) HDPE/ 1 % CNT HDPE HDPE/ 0.8 % CNT ta (° ) Chouit et al. Nanoscale Research Letters 2014, 9:288 Page 5 of 6 http://www.nanoscalereslett.com/content/9/1/288 band at around 1,331 cm−1 originated from atomic dis- placement and disorder caused by structural defect [21]. The second one at around 1,599 cm−1 indicates the graphitic state of bamboo MWNTs. Moreover, the inten- sity ratio of D to G (ID/IG) is measured to be 1.14. This suggests a certain degree of orderly graphitic structure in the prepared nitrogen-doped MWNTs, which is con- sistent with the observed TEM results. The TGA is used to investigate the distribution and species of the carbon phases present in CNTs. Figure 3 shows the derivative of TGA curve of the nitrogen- doped MWNTs. The weight loss is considered due to the combustion of carbon in air atmosphere and repre- sents more than 97% of carbon content for the prepared sample with oxidation peak at 550°C. Consequently, this shift in the mass loss maxima suggests more defects and disorders for the nitrogen-doped MWNTs which are in good agreement with the Raman results. Characterization of nanocomposites (HDPE/N-MWNTs) The SEM images for the nanocomposites were taken without any treatment at two different magnifications. The nanocomposite cross-sectional surface for 0.8 wt.% N-MWCNT content is represented in Figure 4, where the N-MWNT in HDPE is clearly observed even at low loadings of MWNT in the composites. The Raman analysis for this nanocomposite presented in Figure 5 shows the presence of the D and G bands in the background as a result of the relatively low concen- tration of MWNT in polymer. However, the presence of carbon nanostructures can still be easily detected, and their Raman feature peaks are located at similar band- width as the ones in the pristine material. On the other hand, the larger intensity reflections are the bands resulting from the HDPE matrix as reported in the literature [22]. The band at 1,080 cm−1 is used to characterize the level of amorphous phase in HDPE. In- deed, Raman spectroscopy is one of the most powerful tools to characterize the crystallinity of HDPE [22], and this is made through the intensity measurement between 1,400 and 1,460 cm−1. Those bands are characteristics of the methylene bending vibrations. In particular, the band in the 1,418 cm−1 region is typically assigned to that of the orthorhombic crystalline phase in polyethylene [22-24]. Furthermore, Figure 6 shows the X-ray diffraction (XRD) patterns of the pristine HDPE and nanocompos- ites filled with N-MWNTs. The pristine HDPE mainly exhibits a strong reflection peak at 21.6° followed by a less intensive peak at 24.0°, which correspond to the typ- ical orthorhombic unit cell structure of (110) and (200) reflection planes, respectively. These 2θ values are in good agreement with the reported values of polyethylene [10,25,26]. The two weak peaks at 2θ around 30.0° and 36.2° are attributed to reflection planes (210) and (020), respectively [27,28]. In addition, there are several other weak reflection planes in the range of 38° to 60° [28]. The two crystalline characteristic peaks (110) and (200) remain unchanged after the incorporation of the N-MWNTs, in- dicating that the addition of the N-MWNTs did not affect the original crystal structure of the HDPE matrix. Conclusion A melt processing method has been used to prepare HDPE/N-MWNT nanocomposites with different filler loading percentages between 0.1, 0.4, 0.8, and 1.0 wt.%. The CNTs were dispersed into the host HDPE matrix by shearing action only of a pair of cylinder screws and then hot-pressed. HRTEM observations indicate that the N-MWNT product exhibits a bamboo shape with 97% purity and a high selectivity. The presence of N-MWNT in polymer matrix HDPE is clearly observed even at low loadings of N-MWNTs. The fraction of the crystalline phase was determined from the normalized integrated in- tensity of the 1,418 cm−1 Raman band, which represents the orthorhombic crystalline phase in polyethylene. The XRD analysis demonstrated that the crystalline structure of HDPE matrix was not affected by the incorporation of the N-MWNTs. Competing interests The authors declare that they have no competing interests. Authors’ contributions MG conceived the idea and planned the experiments. FC carried out the synthesis of nanocomposites and their characterization and analyzed the data. OG carried out the synthesis of carbon nanotubes and their characterization. NB carried out the Raman spectroscopy and analyzed the data. The manuscript was prepared by FC. NB, OG, MG, and SB, and AH helped with the draft editing and contributed to the preparation and revision of the paper. All authors read and approved the final manuscript. Acknowledgements The authors would like to thank Dr. Francisco C. Robles Hernandez at the University of Houston College of Technology for taking the HRSEM pictures of the HDPE/MWCNT composites. 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Submit your manuscript to a journal and benefi t from: 7 Convenient online submission 7 Rigorous peer review 7 Immediate publication on acceptance 7 Open access: articles freely available online 7 High visibility within the fi eld 7 Retaining the copyright to your article Submit your next manuscript at 7 springeropen.com Abstract Background Methods Materials Nanocomposite preparation Characterization techniques Results and discussions Analysis of carbon nanotubes Characterization of nanocomposites (HDPE/N-MWNTs) Conclusion Competing interests Authors’ contributions Acknowledgements Author details References << /ASCII85EncodePages false /AllowTransparency false /AutoPositionEPSFiles true /AutoRotatePages /PageByPage /Binding /Left /CalGrayProfile (Dot Gain 20%) /CalRGBProfile (sRGB IEC61966-2.1) /CalCMYKProfile (U.S. Web Coated \050SWOP\051 v2) /sRGBProfile (sRGB IEC61966-2.1) /CannotEmbedFontPolicy /Error /CompatibilityLevel 1.4 /CompressObjects /Tags /CompressPages true /ConvertImagesToIndexed true /PassThroughJPEGImages true /CreateJobTicket false /DefaultRenderingIntent /Default /DetectBlends true /DetectCurves 0.1000 /ColorConversionStrategy /LeaveColorUnchanged /DoThumbnails true /EmbedAllFonts true /EmbedOpenType false /ParseICCProfilesInComments true /EmbedJobOptions true /DSCReportingLevel 0 /EmitDSCWarnings false /EndPage -1 /ImageMemory 1048576 /LockDistillerParams true /MaxSubsetPct 100 /Optimize true /OPM 1 /ParseDSCComments true /ParseDSCCommentsForDocInfo true /PreserveCopyPage true /PreserveDICMYKValues true /PreserveEPSInfo true /PreserveFlatness true /PreserveHalftoneInfo false /PreserveOPIComments false /PreserveOverprintSettings true /StartPage 1 /SubsetFonts true /TransferFunctionInfo /Apply /UCRandBGInfo /Preserve /UsePrologue false /ColorSettingsFile () /AlwaysEmbed [ true ] /NeverEmbed [ true ] /AntiAliasColorImages false /CropColorImages true /ColorImageMinResolution 300 /ColorImageMinResolutionPolicy /OK /DownsampleColorImages true /ColorImageDownsampleType /Bicubic /ColorImageResolution 300 /ColorImageDepth -1 /ColorImageMinDownsampleDepth 1 /ColorImageDownsampleThreshold 1.50000 /EncodeColorImages true /ColorImageFilter /DCTEncode /AutoFilterColorImages true /ColorImageAutoFilterStrategy /JPEG /ColorACSImageDict << /QFactor 0.15 /HSamples [1 1 1 1] /VSamples [1 1 1 1] >> /ColorImageDict << /QFactor 0.15 /HSamples [1 1 1 1] /VSamples [1 1 1 1] >> /JPEG2000ColorACSImageDict << /TileWidth 256 /TileHeight 256 /Quality 30 >> /JPEG2000ColorImageDict << /TileWidth 256 /TileHeight 256 /Quality 30 >> /AntiAliasGrayImages false /CropGrayImages true /GrayImageMinResolution 300 /GrayImageMinResolutionPolicy /OK /DownsampleGrayImages true /GrayImageDownsampleType /Bicubic /GrayImageResolution 300 /GrayImageDepth -1 /GrayImageMinDownsampleDepth 2 /GrayImageDownsampleThreshold 1.50000 /EncodeGrayImages true /GrayImageFilter /DCTEncode /AutoFilterGrayImages true /GrayImageAutoFilterStrategy /JPEG /GrayACSImageDict << /QFactor 0.15 /HSamples [1 1 1 1] /VSamples [1 1 1 1] >> /GrayImageDict << /QFactor 0.15 /HSamples [1 1 1 1] /VSamples [1 1 1 1] >> /JPEG2000GrayACSImageDict << /TileWidth 256 /TileHeight 256 /Quality 30 >> /JPEG2000GrayImageDict << /TileWidth 256 /TileHeight 256 /Quality 30 >> /AntiAliasMonoImages false /CropMonoImages true /MonoImageMinResolution 1200 /MonoImageMinResolutionPolicy /OK /DownsampleMonoImages true /MonoImageDownsampleType /Bicubic /MonoImageResolution 1200 /MonoImageDepth -1 /MonoImageDownsampleThreshold 1.50000 /EncodeMonoImages true /MonoImageFilter /CCITTFaxEncode /MonoImageDict << /K -1 >> /AllowPSXObjects false /CheckCompliance [ /None ] /PDFX1aCheck false /PDFX3Check false /PDFXCompliantPDFOnly false /PDFXNoTrimBoxError true /PDFXTrimBoxToMediaBoxOffset [ 0.00000 0.00000 0.00000 0.00000 ] /PDFXSetBleedBoxToMediaBox true /PDFXBleedBoxToTrimBoxOffset [ 0.00000 0.00000 0.00000 0.00000 ] /PDFXOutputIntentProfile (None) /PDFXOutputConditionIdentifier () /PDFXOutputCondition () /PDFXRegistryName () /PDFXTrapped /False /CreateJDFFile false /Description << /ARA /BGR /CHS /CHT /CZE /DAN /DEU /ESP /ETI /FRA /GRE /HEB /HRV /HUN /ITA /JPN /KOR /LTH /LVI /NLD (Gebruik deze instellingen om Adobe PDF-documenten te maken voor kwaliteitsafdrukken op desktopprinters en proofers. 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