Study of the morphology and granulometry of polyethylene–clay nanocomposite powders

Medium‐density polyethylene (MDPE) matrix nanocomposites reinforced with different clay contents were produced by using a planetary ball mill. The morphology of all the milled samples, including pure polyethylene and the polyethylene–clay nanocomposites, was examined by scanning electron microscopy. To investigate the effects of milling time and clay content on the particle size of polyethylene powder, sieve analysis was used. The results showed that during milling, the regular shape of pure polyethylene powder converts into flake shapes and the average particle size of the powder increases upon increasing the milling time because the welding mechanism is predominant. Also, the presence of the clay can increase the maximum‐particle size, and increasing the clay content can decrease the milling time required to reach the same maximum particle size. J. VINYL ADDIT. TECHNOL., 2010. © 2009 Society of Plastics Engineers     

The effect of ball milling time and rotational speed on ultra high molecular weight polyethylene reinforced with multiwalled carbon nanotubes

Ultra high molecular weight polyethylene (UHMWPE) composites reinforced with multiwalled carbon nanotubes (MWCNT) were produced using planetary ball milling. The aim was to develop a more wear resistant composite with improved mechanical properties to be used in stress bearing joints. The effect of manufacturing parameters such as the effect of ball milling time and rotational speed on the final composite was analyzed by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), particle size distribution, and contact angle measurements. Ball milling as a mixing technique for UHMWPE based composites is not a new approach but yet, the effect of time, rotational speed, loading of milling jar, and type of ball mill has not been reported properly for UHMWPE. Composites with 0.5 and 1.0 wt% UHMWPE/MWCNTs were manufactured with different rotational speed and mixing times. The results indicate that rotational speed rather than mixing time is important for dispersing MWCNTs using planetary ball milling. Tensile test showed a slight decrease for the MWCNT concentration of 1 wt% suggesting that this amount is the threshold for a satisfactory distribution of the fillers in the matrix. POLYM. COMPOS. 37:1128–1136, 2016. © 2014 Society of Plastics Engineers     

Properties of carbon nanotube reinforced linear low density polyethylene nanocomposites fabricated by cryogenic ball‐milling

A cryogenic ball‐milling process to produce polymer/CNT nanocomposites was investigated. Linear low density polyethylene was used as the matrix material and 1 wt % of multiwalled carbon nanotubes (MWCNT) was used as reinforcement. The influence of the milling time and balls size was evaluated. The morphology of the nanocomposite and the degree of dispersion of the MWCNTs were studied using scanning electron microscopy (SEM), visual inspection, and light transmission microscopy; ropes as well as aggregates of MWCNTs were observed, and there was evidence of wetting of the nanotubes by the matrix polymer. An increase of up to 28% in the elastic modulus (determined by tensile testing) with respect to the matrix was obtained. Differential scanning calorimetry (DSC) analysis showed evidence of increase in the degree of crystallization, a result of the nucleating capability of the carbon nanotubes in the matrix. The degradation temperature of the nanocomposites does not show significant variations with respect to the unfilled polymer. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

On the Dependence of Avrami Indexes of MDPE on Milling Time

In the current study, the role of milling time on thermal properties and crystallization behavior of medium density polyethylene (MDPE) was investigated. For this purpose, high energy ball mill and differential scanning calorimetry (DSC) techniques were used. The results of DSC tests indicated that the milling process affected on crystallization behavior and thermal properties of MDPE. Rising crystallization temperature, specific heat capacity and crystallinity index and decreasing Avrami index were caused by ball milling; yet melting temperature was not changed, even at long milling times. In summary, thermal properties of the polymer were not changed significantly by increasing milling time.     

Preparation and characterization of multi‐walled carbon nanotube/poly(ethylene terephthalate) nanoweb

Multi‐walled carbon nanotube (MWCNT)/Poly(ethylene terephthalate) (PET) nanowebs were obtained by electrospinning. For uniform dispersion of MWCNTs in PET solution, MWCNTs were functionalized by acid treatment. Introduction of carboxyl groups onto the surface of MWCNTs was examined by Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) analysis. MWCNTs were added into 22 wt % PET solution in the ratio of 1, 2, 3 wt % to PET. The morphology of MWCNT/PET nanoweb was observed using field emission‐scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM). The nanofiber diameter decreased with increasing MWCNT concentration. The distribution of the nanofiber diameters showed a bi‐modal shape when MWCNTs were added. Thermal and tensile properties of electrospun MWCNT/PET nanowebs were examined using a differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA) and etc. Tensile strength, tensile modulus, thermal stability, and the degree of crystallinity increased with increasing MWCNT concentration. In contrast, elongation at break and cold crystallization temperature showed a contrary tendency. Electric conductivities of the MWCNT/PET nanowebs were in the electrostatic dissipation range. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improved dielectric performance of polypropylene/multiwalled carbon nanotube nanocomposites by solid‐phase orientation

By means of a die‐drawing technique in the rubbery state, the effect of the orientation of the microstructure on the dielectric properties of polypropylene (PP)/multiwalled carbon nanotube (MWCNT) nanocomposites was examined in this study. The viscoelastic behavior of the PP/MWCNT nanocomposites with MWCNT weight loadings ranging from 0.25 to 5 wt % and the dielectric performance of the stretched PP/MWCNT nanocomposites at different drawing speeds and drawing ratios were studied to obtain insight into the influences of the dispersion and orientation state of the MWCNTs and matrix molecular chains. A viscosity decrease (ca. 30%) of the PP/MWCNT‐0.25 wt % (weight loading) melt was obviously due to the free volume effect. Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction were adopted to detect the orientation structure and the variation of crystal morphology of the PP/MWCNTs. Melting plateau regions, which indicated the mixed crystallization morphology for the stretched samples, were found in the DSC patterns instead of a single‐peak for the unstretched samples. We found that the uniaxial stretching process broke the conductive MWCNT networks and consequently increased the orientation of MWCNTs and molecular chains along the tensile force direction; this led to an improvement in the dielectric performance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42893.     

Ethylene‐vinyl acetate copolymer/multiwalled carbon nanotube/organoclay nanocomposites

Ethylene‐vinyl acetate copolymer (EVA) was melt‐mixed with multiwalled carbon nanotubes (MWCNTs) and organoclays, and the effects of simultaneous use of organoclays and MWCNTs on the surface resistivity and tensile properties of EVA nanocomposites were investigated. The surface resistivity of EVA/MWCNT nanocomposite with 1 phr of MWCNT is out of our measurement range (above 10¹² Ω/square). With increasing content of organoclay from 0 to 3 phr, the surface resistivity of the EVA/MWCNT/organoclay nanocomposites with 1 phr MWCNT remains out of our measurement range. However, the surface resistivity of the nanocomposite decreases to 10⁶ Ω/square with addition of 5 phr organoclay. The tensile properties of EVA/MWCNT/organoclay nanocomposites with 1 phr MWCNT and 5 phr organocaly are similar to those of EVA/MWCNT nanocomposites with 5 phr MWCNT except tensile modulus. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

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     

Multiwall‐carbon‐nanotube‐reinforced poly(ethylene terephthalate) nanocomposites by melt compounding

Poly(ethylene terephthalate) (PET) nanocomposites reinforced with multiwall carbon nanotubes (MWCNTs) were prepared through melt compounding in a twin‐screw extruder. The presence of MWCNTs, which acted as good nucleating agents, enhanced the crystallization of PET through heterogeneous nucleation. The incorporation of a small quantity of MWCNTs improved the thermal stability of the PET/MWCNT nanocomposites. The mechanical properties of the PET/MWCNT nanocomposites increased with even a small quantity of MWCNTs. There was a significant dependence of the rheological properties of the PET/MWCNT nanocomposites on the MWCNT content. The MWCNT loading increased the shear‐thinning nature of the polymer‐nanocomposite melt. The storage modulus and loss modulus of the PET/MWCNT nanocomposites increased with increasing frequency, and this increment effect was more pronounced at lower frequencies. At higher MWCNT contents, the dominant nanotube–nanotube interactions led to the formation of interconnected or networklike structures of MWCNTs in the PET/MWCNT nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1450–1457, 2007     

in situ synthesis of biopolyurethane nanocomposites reinforced with modified multiwalled carbon nanotubes

Biopolyurethane nanocomposites reinforced with silane‐modified multiwalled carbon nanotubes (s‐MWCNT) were successfully prepared. The carbon nanotube surfaces were modified by means of functional amine groups via ozone oxidation followed by silanization. The surface structure of the s‐MWCNTs was characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. The s‐MWCNTs were incorporated into a vegetable oil‐based polyurethane (PU) network via covalent bonding to prepare PU nanocomposites. The effect of s‐MWCNT loading on the morphology, thermomechanical, and tensile properties of the PU nanocomposites was studied. It was determined that the s‐MWCNTs were dispersed effectively in the polymer matrix and that they improved the interfacial strength between the reinforcing nanotubes and the polymer matrix. Storage modulus, glass transition temperature, Young's modulus, and tensile strength of the nanocomposites increased with increasing s‐MWCNT loading up to 0.8%. However, increasing the s‐MWCNT content to 1.2 wt % resulted in a decrease in thermomechanical properties of the PU nanocomposites. This effect was attributed to the fact that at high s‐MWCNT contents, the increased number of amine groups competed with the polyol's hydroxyl groups for isocyanate groups, causing a decrease in the integrity of the PU matrix. High s‐MWCNT contents also facilitated aggregation of the nanotubes, causing a decrease in thermomechanical properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42515.     

Increasing the thermal conductivity of palmitic acid by the addition of carbon nanotubes

Four different methods, acid oxidation, mechanochemical reaction, ball milling, and grafting following acid oxidation, were used to treat multi-walled carbon nanotubes (MWCNTs). During treatment, hydroxyl groups, carboxylic groups, and amidocyanogen were introduced onto the surfaces of the MWCNTs. The MWCNTs were dispersed into palmitic acid (PA) to prepare phase change composites with high thermal conductivity. Both chemical treatment and ball milling help to break the MWCNT aggregates and to enhance their dispersibility. Measurements show that the thermal conductivity increase of the composites is highly dependent on the MWCNT pretreatment process. We propose that the difference in the interfacial thermal resistance between the MWCNTs and the matrix is due to the difference of the MWCNT surface state caused by different treatment processes. In all the MWCNT/PA composites, the one containing MWCNTs with hydroxyl groups, treated by a mechanochemical reaction, has the highest thermal conductivity increase, which, at room temperature, is up to 51.6% for a MWCNT addition of 1.0%.     

The enhanced mechanical properties of a covalently bound chitosan‐multiwalled carbon nanotube nanocomposite

In the present work, chitosan (CS)‐grafted multiwalled carbon nanotube (MWCNT) nanocomposites were prepared via covalently bonded CS onto MWCNTs that had weight fractions of MWCNTs ranging from 0.1 to 3.0 wt % by a simple method of solution casting. The structure, morphology, and mechanical properties of the films were investigated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, optical microscopy, wide‐angle X‐ray diffraction, contact angle, and tensile testing. The results indicated that the CS chains were attached onto the MWCNTs successfully via covalent linkages. More interestingly, the MWCNTs provided a matrix that facilitated the crystallization of CS. Compared with the pure CS, the tensile strength and Young's modulus of the nanocomposites were enhanced significantly from 39.6 to 105.6 MPa and from 2.01 to 4.22 GPa with an increase in the MWCNT loading level from 0 to 3.0 wt %, respectively. The improvement in the tensile strength and modulus were ascribed to the uniform dispersion of MWCNTs covalently linked to the CS matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of the viscosity and processing parameters on the surface resistivity of polypropylene/multiwalled carbon nanotube and ethylene–propylene–diene/multiwalled carbon nanotube nanocomposites

In this study, relatively large amounts of polypropylene (PP) and ethylene–propylene–diene (EPDM) were melt‐mixed with multiwalled carbon nanotubes (MWCNTs). Although the melt‐compounding method has many advantages, the uniform dispersion of carbon nanotubes in the polymer matrix is still the most challenging task. Because the electrical conductivity of composites is strongly influenced by the filler's state of dispersion and the extent of filler breakage during processing, the effects of the viscosity and processing conditions, such as the mixing time, rotor speed, and cooling rate, on the surface resistivity were studied. The PP/MWCNT nanocomposites displayed a high dependence of surface resistivity on the cooling rate, and the EPDM/MWCNT nanocomposites displayed a higher surface resistivity at the same content of MWCNTs and less dependence of surface resistivity on the cooling rate compared with PP/MWCNT nanocomposites. The increased surface resistivity of the EPDM/MWCNT nanocomposites was observed when EPDM with higher viscosity was used to prepare the EPDM/MWCNT nanocomposites. By increasing the rotor speed, lower surface resistivity was obtained in the PP/MWCNT nanocomposites. However, by increasing the rotor speed, a higher surface resistivity was obtained in the EPDM/MWCNT nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrical and mechanical tuning of 3D printed photopolymer–MWCNT nanocomposites through in situ dispersion

An electric field-assisted in situ dispersion of multiwall carbon nanotubes (MWCNTs) in polymer nanocomposites, fabricated through stereolithography three-dimensional (3D) printing technique, was demonstrated. The introduction of MWCNTs increased the elasticity modulus of the polymer resin by 77%. Furthermore, the use of an electric field for in situ MWCNT dispersion helped improving the average elongation at break of the samples with MWCNTs by 32%. The electric field also increased the ultimate tensile strength of the MWCNT reinforced nanocomposites by 42%. An increase of over 20% in the ultimate tensile strength of in situ dispersed MWCNT nanocomposites over the pure polymer material was observed. Finally, it was demonstrated that the magnitude and direction of the electrical conductivity of MWCNT nanocomposites can be engineered through the application of in situ electric fields during 3D printing. An increase of 50% in the electrical conductivity was observed when MWCNTs were introduced, while the application of the electric field further improved the electrical conductivity by 26%. The presented results demonstrated the feasibility of tuning both electrical and mechanical properties of MWCNT reinforced polymer nanocomposites using in situ electrical field-assisted 3D printing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47600.     

Effect of organoclay content on the mechanical properties of ethylene‐vinyl acetate copolymer/ multi‐walled carbon nanotube/organoclay foams

The main objective of this study is to obtain ethylene‐vinyl acetate copolymer (EVA)/multi‐walled carbon nanotube (MWCNT)/organoclay foams with improved mechanical properties without increase of their density, compared with EVA/MWCNT foams. MWCNT content was fixed at 5 phr in this study. To achieve the objective, EVA was melt‐mixed with MWCNTs and organoclays in a bench kneader. And the obtained EVA/MWCNT/organoclay mixtures were mixed with chemical blowing agent and cross‐linking agent in a two roll‐mill. After being mixed in a two roll‐mill, the mixtures were put in a mold and the foams were obtained by compression‐molding. The effect of organoclay content on the mechanical properties and surface resistivity of EVA/MWCNT (5 phr)/organoclay foams was investigated. The addition of 1 phr organoclays to the EVA/MWCNT (5 phr) foams resulted in the improvement of tensile strength, 100% tensile modulus, tear strength, and compression set without increase of the density. However, further increase in content of organoclay (3 phr) leaded to a deterioration of mechanical properties. Therefore, determining the optimal content of organoclay was very important in order to achieve the main objective of this study. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Dispersion of multiwalled carbon nanotubes in polyacrylonitrile‐co‐starch copolymer matrix for enhancement of electrical,thermal, and gas barrier properties

Nanomaterials gained great importance on account of their wide range of applications in many areas. Carbon nanotubes (CNTs) exhibit exceptional electrical, thermal, gas barrier, and tensile properties and can therefore be used for the development of a new generation of composite materials. Functionalized multiwalled carbon nanotubes (MWCNTs) reinforced Polyacrylonitrile‐co‐starch nanocomposites were prepared by in situ polymerization technique. The structural property of PAN‐co‐starch/MWCNT nanocomposites was studied by X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The conductivity, tensile strength, and thermal properties of nanocomposites were measured as a function of MWCNT concentrations. The thermal stability, conductivity, and tensile strength of PAN‐co‐starch/MWCNT nanocomposites were improved with increasing concentration of MWCNTs. Oxygen barrier property of PAN‐co‐starch/MWCNT nanocomposites was calculated and it was found that, the property was reduced substantially with increase of MWCNTs proportion. The synthesized PAN‐co‐starch/MWCNT nanocomposites may used for electrostatically dissipative materials, aerospace or sporting goods, and electronic materials. © 2013 Society of Plastics Engineers     

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.     

Cellulose acetate/multiwalled carbon nanotube nanocomposites with improved mechanical,thermal, and electrical properties

Cellulose acetate (CA)‐based nanocomposites with various contents of neat multiwalled carbon nanotube (MWCNT) or acid‐treated one (MWCNT‐COOH) are prepared via melt‐compounding method and investigated their morphology, thermal stability, mechanical, and electrical properties. SEM microphotographs reveal that MWCNT‐COOHs are dispersed uniformly in the CA matrix, compared with neat MWCNTs. FTIR spectra support that there exists a specific interaction between carboxyl groups of MWCNT‐COOHs and ester groups of CA, indicating good interfacial adhesion between MWCNT‐COOHs and CA matrix. Accordingly, thermal stability and dynamic mechanical properties of CA/MWCNT‐COOH nanocomposites were higher than those of CA/MWCNT composites. On the contrary, electrical volume resistivities of CA/MWCNT‐COOH nanocomposites are found to be somewhat higher than those of CA/MWCNT composites, which is because of the deterioration of graphene structures for MWCNT‐COOHs and the good dispersion of MWCNT‐COOHs in the CA matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological and thermal properties of poly(ethylene oxide)/multiwall carbon nanotube composites

Poly(ethylene oxide) (PEO) based nanocomposites were prepared by the dispersion of multiwall carbon nanotubes (MWCNTs) in aqueous solution. MWCNTs were added up to 4 wt % of the PEO matrix. The dynamic viscoelastic behavior of the PEO/MWCNT nanocomposites was assessed with a strain‐controlled parallel‐plate rheometer. Prominent increases in the shear viscosity and storage modulus of the nanocomposites were found with increasing MWCNT content. Dynamic and isothermal differential scanning calorimetry studies indicated a significant decrease in the crystallization temperature as a result of the incorporation of MWCNTs; these composites can find applications as crystallizable switching components for shape‐memory polymer systems with adjustable switching temperatures. The solid‐state, direct‐current conductivity was also enhanced by the incorporation of MWCNTs. The dispersion level of the MWCNTs was investigated with scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

碳纳米管/纤维素在不饱和聚酯树脂中的分散性及力学性能研究

在超声改善MWCNT在不饱和聚酯树脂的分散性的基础上,通过非共价官能团化的方法引入处理过的天然填料柠檬酸化纤维素(CNFCA)来增强不饱和聚酯树脂,并采用偏光显微镜、旋转流变仪、透射电子显微镜、扫描电子显微镜、万能试验机等对不饱和聚酯树脂纳米复合材料的结构和性能进行了研究.结果表明,MWCNT的加入可以使不饱和聚酯复合...