Influence of silane concentration on the silanization of multiwall carbon nanotubes

The relationship between the concentration of silane, the degree of surface coverage and the functionalization of multiwall carbon nanotubes (MWCNTs) upon silanization is experimentally investigated. MWCNT silanization is conducted using a γ-methacryloxypropyltrimethoxy silane varying its concentration with respect to the weight of the MWCNTs from 3.5% to 1000% (10×). Physicochemical characterization of the MWCNTs points out that the optimum range of silane concentration required to generate adequate surface coverage on the MWCNTs is between one and two times the weight of the MWCNTs. This optimum range of silane concentration is further confirmed by mechanical testing of silanized MWCNT/vinyl ester polymer composites.     

Synthesis and characterization of functionalized carbon nanotubes with different wetting behaviors and their influence on the wetting properties of carbon nanotubes/polymethylmethacrylate coatings

The synthesis and characterization of hydrophobic functionalized multi-wall carbon nanotubes (MWCNTs) were investigated and their influence on the wetting properties of organic coatings and composites was studied. Functionalization was performed using oxidation, 1,3-dipolar cycloaddition, and silanization. Silanization was conducted using three hydrophobic silane precursors: 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, and triethoxyoctylsilane. Functionalization was directly confirmed and characterized by Fourier transform infrared spectroscopy, thermal gravimetric analysis, and scanning electron microscopy. The water contact angle of the functionalized MWCNTs was 40–142° for different surface functionalities and the functionalized MWCNTs were incorporated into an acidic solution of polymethylmethacrylate. The effect of surface functionality and the concentration of the functionalized MWCNTs on the wetting properties of these composites were studied by measuring the water contact angle. Under optimum conditions, composite surfaces with water contact angles greater than 110° were obtained. Atomic force microscopy was used to determine the topography of the surface and energy dispersion spectroscopy was used to determine the distribution of the functionalized MWCNTs in the composite film. It was shown that the hydrophobic functionalized MWCNTs migrated to the surface; this was more pronounced for the more hydrophobic MWCNTs.     

Supercritical carbon dioxide-assisted silanization of multi-walled carbon nanotubes and their effect on the thermo-mechanical properties of epoxy nanocomposites

Supercritical carbon dioxide was employed as the solvent for the functionalization of multi-walled carbon nanotubes (MWCNTs) with an epoxy-capped silane. The silanization protocol was found to be a suitable green alternative to traditional routes that rely on organic solvents for grafting nearly monolayers of silane molecules onto the nanotube surfaces. The addition of silanized MWCNTs to a model epoxy markedly increased its T_g, and measurements of the network cooperativity length scale linked this change to a reduction in polymer segment mobility. Composites filled with low loading levels of both pristine and silanized MWCNTs exhibited significantly higher strain at break and toughness than the neat epoxy, and the greatest improvements were observed at low loading levels. SEM analysis of the composite fracture surfaces revealed that nanotube pullout was the primary failure mechanism in epoxy loaded with pristine MWCNTs while crack bridging predominated in composites containing silanized MWCNTs as the result of strong interfacial bonding with the matrix. The elevated T_g and toughness achieved with small additions of silanized MWCNTs promise to extend the engineering applications of the epoxy resin.     

An Insight into the Silanization of Montmorillonite Nanoparticles

The purpose of this study is to investigate the effect of reaction conditions on the silanization of montmorillonite nanoparticles using methacryloxypropyltrimethoxysilane (γ–MPS) and to establish relationships between the reaction conditions, the grafting percentage, and the silane arrangement on the particles. The silanization reaction was performed in the following conditions: (i) acidic ethanol-water solution with a pH of 5 and (ii) basic cyclohexane with a pH of 9. To characterize the surface of montmorillonite nanoparticles, analytical methods such as Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), CHN elemental analysis, and X-ray diffraction (XRD) diffraction were utilized. In addition, the dispersion stability of modified particles suspended in different solvents was investigated using a separation analyzer. The results revealed silane grafting in cyclohexane (pH?=?9) achieved higher silanization efficiency, leading to a larger basal spacing in montmorillonite nanoparticles. A parallel arrangement was also suggested for the silane molecules on the surface of the nanoparticles. The higher hydrophobicity of the modified nanoparticles and the decreased overall density of the grafted particles led to a better dispersion in ethanol and toluene.     

Effect of silane structure on the properties of silanized multiwalled carbon nanotube-epoxy nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were functionalized with aminosilanes via an aqueous deposition route. The size and morphology of siloxane oligomers grafted to the MWCNTs was tuned by varying the silane functionality and concentration and their effect on the properties of a filled epoxy system was investigated. The siloxane structure was found to profoundly affect the thermo-mechanical behavior of composites reinforced with the silanized MWCNTs. Well-defined siloxane brushes increased the epoxy T_g by up to 19 °C and significantly altered the network relaxation dynamics, while irregular, siloxane networks grafted to the MWCNTs had little effect. The addition of both types of silanized MWCNTs elicited improvements in the strength of the nanocomposites, but only the well-defined siloxane brushes engendered dramatic improvements in toughness. Because the silanization reaction is simple, rapid, and performed under aqueous conditions, it is also an industrially attractive functionalization route.     

The effect of multiwall carbon nanotubes on the properties of room temperature-vulcanized silicone adhesives

The effects of surface-functionalized and pristine multiwall carbon nanotubes (MWCNT) on the bulk and adhesion properties of silicone nanocomposites were investigated. The MWCNTs surface functionalization was carried out by silanization of methacryloxy or vinyl-based silanes. The nanocomposites were prepared using solvent mixing which enhanced distribution and dispersion of the MWCNTs in the high-viscosity silicone matrix. The quality of dispersion was evaluated using scanning electron microscopy (SEM) indicating good dispersion state. It was found that the optimal concentration of both treated and untreated MWCNTs in the nanocomposites was 1 wt.%. Above this threshold value, the nanocomposites properties were reduced. Furthermore, the silane treatment of the MWCNTs was proven to be an effective process that resulted in a significant increase in the nanocomposites properties compared to the neat polymer, leading to higher storage modulus simultaneously with up to 27% improvement in the tensile strength and elongation, 20–30% reduction in the thermal expansion coefficient, 220–300% enhancement in crystallinity (enthalpy of fusion), and up to 56% improvement in the lap shear strength. SEM analysis indicated that significant changes in the fracture morphologies occurred due to higher energy absorption in the case of silane-treated MWCNTs. It was concluded that incorporation of silane-treated MWCNTs is an effective route to reinforce and increase the toughness of silicone-based adhesives.     

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.     

Influence of silanized low‐dimensional carbon nanofillers on mechanical,thermomechanical, and crystallization behaviors of poly(L‐lactic acid) composites—A comparative study

Composites were investigated regarding the comparison of multi‐walled carbon nanotubes (MWCNTs) with exfoliated graphene(EG) in poly(L‐lactic acid) (PLLA) and the effect of silane‐treated carbon nanofillers on properties of PLLA composites. Solution blending method was used to prepare PLLA composites at a filler content of 0.5 wt %. Fourier transform infrared spectroscopy and X‐ray photoelectron spectra results indicated the attachment of silane molecules on the surface of these nanofillers. It was found that the addition of these nanofillers greatly enhanced the mechanical, thermomechanical, and crystallization behaviors of PLLA due to the heterogeneous nucleation effect. Moreover, the silane‐treated fillers further enhanced the breaking elongation moderately (although the materials are still brittle), modulus and thermal property of the nanocomposites, without sacrificing the tensile strength, compared with the pristine nanocomposites. On the other hand, composites reinforced with MWCNTs and EG perform almost the same mechanical property. And EG outperformed MWCNTs in thermomechanical properties of composites when being used as the reinforcement of PLLA. Conversely, composites reinforced with MWCNTs showed better crystallization properties than those reinforced with EG. Interestingly, no significant changes were observed for the crystallization properties of PLLA composites when MWCNTs and EG had been treated by silane coupling agent. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1194‐1202, 2013     

碳纳米管/苯丙乳液导电内墙涂料的制备

先利用混酸体系和3-氨丙基三乙氧基硅烷偶联剂(KH550)对多壁碳纳米管(MWCNTs)进行表面修饰,然后将修饰后的MWCNTs加入苯丙乳液中,成功制备了具有良好抗静电性能和力学性能的碳纳米管/苯丙乳液改性内墙涂料。利用透射电镜,对修饰前后的MWCNTs进行了热重分析。结果表明:KH550成功地接枝到MWCNTs表面,修饰后的MWCNTs能实现很好的分散。研究了MWCNTs用量对所制备涂料的导电性能、力学性能的影响。研究表明当MWCNTs添加量达到2.50%时,涂料的表面电阻最小,为1.42×107Ω,力学性能最佳。     

Design and evaluation of the interface between carbon nanotubes and natural rubber

To design the interface between carbon nanotubes and natural rubber (NR), a silane coupling agent, bis(3‐triethoxysilylpropyl) tetrasulfide (TESPT), was used to modify the surface of multiwalled carbon nanotubes (MWCNTs) in a two‐step method, and the silane‐modified multiwalled carbon nanotubes (s‐MWCNTs) were combined with NR by solvent casting. The s‐MWCNTs with an amorphous layer were visualized by transmission electron microscopy, the functional groups of which were confirmed by Raman and Fourier transform infrared analyses, and the functionalization degree was characterized by thermogravimetric analysis. The interface between s‐MWCNTs and NR was investigated by Raman analysis and field emission scanning electron microscopy (FESEM). Raman analysis showed a shift from 1,340 to 1,353 cm⁻¹ of D band of s‐MWCNTs in the NR/s‐MWCNT composite, and FESEM observation indicated that s‐MWCNTs were embedded deeply in NR. All of these results proved that s‐MWCNTs were grafted with TESPT and they reacted with the active double bonds of NR to form a strong interface. The improved interface resulted in an extreme nonlinear viscoelastic behavior and enhanced dynamic mechanical property of NR/s‐MWCNT composite as compared to NR/MWCNT composite. POLYM. COMPOS., 2011. © 2010 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     

Preparation of MEMO silane-coated SiO2 nanoparticles under high pressure of carbon dioxide and ethanol

The objective of this study is to investigate and compare methods of nanosilica coating with γ-methacryloxypropyltrimethoxy (MEMO) silane using supercritical carbon dioxide and carbon dioxide-ethanol mixture. Characterization of grafted silane coupling agent on the nanosilica surface was performed by the infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The d₅₀ value and particle size distribution were determined by laser particle size analyzer (PSA). The operating parameters of silanization process at 40 °C, such as the silica/silane weight ratio, the presence of ethanol, and the pressure, were found to be important for the successful coating of silica particles with minimum agglomeration. The results indicate that presence of ethanol in high-pressure carbon dioxide plays an important role in achieving successful deagglomeration of coated nanoparticles. Dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM) revealed that dispersion of the silica particles in the PMMA matrix and interfacial adhesion between silica particles and polymer matrix were enhanced, when silica nanoparticles treated with silane under high pressure of carbon dioxide and ethanol were used for the nanocomposite preparation.     

Enhanced Thermal Conductivity of Epoxy Composites with MWCNTs/AlN Hybrid Filler

To further improve the thermal conductivity of epoxy resin, the multi-walled carbon nanotube/aluminum nitride (MWCNTs/AlN) hybrid filler was employed to prepare thermal conductivity MWCNTs/AlN/epoxy composite by casting process, and the silane coupling reagent of γ-glycidoxy propyl trimethoxy silane(KH-560) was also used to functionalize the surface of MWCNTs and/or AlN. Results revealed that, the thermal conductivity of epoxy resin was improved remarkably with the addition of MWCNTs/AlN hybrid filler, a higher thermal conductivity of 1.04 W/mK could be achieved with 29 wt% MWCNTs/AlN hybrid filler (4 wt% MWCNTs +25 wt% AlN), about 5 times higher than that of native epoxy resin. And the epoxy composite with 29 wt% MWCNTs/AlN hybrid filler possessed better thermal conductivity and mechanical properties than those of single 5 wt% MWCNTs or 40 wt% AlN. The thermal decomposition temperature of MWCNTs/AlN/epoxy composite was increased with the addition of MWCNTs/AlN hybrid filler. For given filler loading, surface treatment of MWCNTs and/or AlN by KH-560 exhibited a positive effect on the thermal conductivity of epoxy composite.     

Influence of aminosilane‐functionalized carbon nanotubes on the rheometric,mechanical, electrical and thermal degradation properties of epoxidized natural rubber nanocomposites

We describe the preparation, characterization and physical properties of multiwalled carbon nanotube (MWCNT)‐filled epoxidized natural rubber (ENR) composites. To ensure better dispersion in the elastomer matrix, the MWCNTs were initially subjected to aminopropyltriethoxysilane (APS) treatment to bind amine functional groups (?NH₂) on the nanotube surface. Successful grafting of APS on the MWCNT surface through Si–O–C linkages was confirmed using Fourier transform infrared spectroscopy. Grafting of APS on the MWCNT surface was further corroborated using elemental analysis. ENR nanocomposites with various filler loadings were prepared by melt compounding to generate pristine and APS‐modified MWCNT‐filled elastomeric systems. Furthermore, we determined the effects of various filler loadings on the rheometric, mechanical, electrical and thermal degradation properties of the resultant composite materials. Rheometric cure characterization revealed that the torque difference increased with pristine MWCNT loading compared to the gum system, and this effect was more pronounced when silane‐functionalized MWCNTs were loaded, indicating that this effect was due to an increase in polymer–carbon nanotube interactions in the MWCNT‐loaded materials. Loading of silane‐functionalized MWCNTs in the ENR matrix resulted in a significant improvement in the mechanical, electrical and thermal degradation properties of the composite materials, when compared to gum or pristine MWCNT‐loaded materials.© 2013 Society of Chemical Industry     

Improvement of the Properties of PC/LCP/MWCNT with or without Silane Coupling Agents

Present study concentrates on the effect of silane coupling agent on the properties and dispersibility of multi-walled carbon nanotube (MWCNTs) in the Polycarbonate (PC)/Liquid Crystalline Polymer (LCP) system. Thermal stability of the PC/LCP/MWCNTs has been improved in an appreciable manner with the addition of silane coupling agents, as revealed from thermogravimetric analysis. Storage modulus also enhanced on addition of silane coupling agent into PC/LCP/MWCNTs systems. Field Emission Electron Microscopic study revealed finer morphology and substantial reduction of the LCP domain, indicating better compatibility between PC and LCP in the presence of a silane coupling agent. High Resolution Transmission Electron Microscopic study supports the unform dispersion of MWCNTs throughout the matrix in the presence of a silane coupling agent.     

Characterization of the surface energies of functionalized multi-walled carbon nanotubes and their interfacial adhesion energies with various polymers

The surface energies of pristine multi-walled carbon nanotubes (MWCNTs) and MWCNTs functionalized with carboxylic acid (MWCNT-COOH), acyl chloride and ethyl amine were characterized, and the effects of the changes in MWCNT surface energies on the interfacial adhesion and reinforcement of the composites were explored. When the surface energy of pristine MWCNTs was compared to that of functionalized MWCNTs, a decrease in the dispersive surface energy and an increase in the polar surface energy were observed. Interfacial adhesion energies between MWCNTs and various polymers were estimated from surface energy values of MWCNTs and various polymers. Among the MWCNTs, polyethylene, polystyrene and bisphenol-A polycarbonate (PC) had the highest interfacial energy with pristine MWCNTs, while nylon 6,6 and polyacrylamine exhibited the highest interfacial energy with MWCNT-COOH. When tensile properties and adhesion at the interface of PC and nylon 6,6 composites containing MWCNTs were examined, composites having high interfacial adhesion energy exhibited greater adhesion at the interface and reinforcement.     

Tailoring in thermomechanical properties of ethylene propylene diene monomer elastomer with silane functionalized multiwalled carbon nanotubes

The incorporation of silane treated multiwalled carbon nanotubes (S‐MWCNTs) is used as an effective path for tailoring thermomechanical properties of ethylene propylene diene monomer (EPDM). In this study, S‐MWCNTs were introduced into EPDM using internal dispersion kneader and two roller mixing mill. By altering the mass ratio of S‐MWCNTs from 0 to 1, thermal conductivity, thermal stability and phase transition temperatures and their respective enthalpies are discussed of the fabricated nanocomposites. It is observed that silane modification improves their dispersion and increases the interfacial bonding between MWCNTs and polymer matrix. Scanning electron microscopy along energy dispersive spectroscopy analysis is performed to confirm the silane functionalized MWCNTs are selectively distributed in the host polymer. More importantly, an important increase in mechanical properties like ultimate tensile strength and hardness is achieved through introducing silane functionalized MWCNTs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43221.     

The effect of surface functionalization of carbon nanotubes on properties of natural rubber/carbon nanotube composites

The objective of this study was to prepare natural rubber composites filled with carbon nanotubes (CNTs) that show an electrical percolation threshold at very low CNT concentrations. Therefore, two methods of surface functionalization of CNTs were investigated to enable an improved dispersion of CNTs and chemical interaction between CNTs and rubber matrix. On one hand, the CNTs have been functionalized ex situ by acid treatment and silanization reaction with bis(triethoxysilylpropyl) tetrasulfide before mixing with the rubber and otherwise in situ functionalization was directly carried out during the processing of the composites in the internal mixer. The grafting of silane molecules onto CNT surface was established by Fourier transform infrared spectroscopy and scanning electron microscopy. Tensile tests revealed the outstanding properties of composites prepared by in situ silanization method. The in situ silanization led to a better dispersion of the CNTs and the formation of chemical linkages between CNT surface and rubber and this became manifest in higher reinforcement of the rubber, higher crosslink densities, and a lower electrical percolation threshold. It was also shown that the in situ silanization is retarding the vulcanization reaction. POLYM. COMPOS., 36:2113–2122, 2015. © 2014 Society of Plastics Engineer     

Fabrication of superhydrophobic surfaces with non-aligned alkyl-modified multi-wall carbon nanotubes

Films of superhydrophobic multi-wall carbon nanotubes (MWCNTs) have been obtained by using alkyl-modified MWCNTs (MWCNT(COOC₁₈H₃₇)_n) and a simple and effective preparation method. The films show both a high contact angle and a small sliding angle for water droplets. A particular characteristic is that on the superhydrophobic surface the alkyl-modified MWCNTs are not intentionally aligned, thus avoiding the preparation techniques using aligned carbon nanotubes to produce the same effect.     

Surface tension of Nanofluid-type fuels containing suspended nanomaterials

ABSTRACT: The surface tension of ethanol and n-decane based nanofluid fuels containing suspended aluminum (Al), aluminum oxide (Al2O3), and boron (B) nanoparticles as well as dispersible multi-wall carbon nanotubes (MWCNTs) were measured using the pendant drop method by solving the Young-Laplace equation. The effects of nanoparticle concentration, size and the presence of a dispersing agent (surfactant) on surface tension were determined. The results show that surface tension increases both with particle concentration (above a critical concentration) and particle size for all cases. This is because the Van der Waals force between particles at the liquid/gas interface increases surface free energy and thus increases surface tension. At low particle concentrations, however, addition of particles has little influence on surface tension because of the large distance between particles. An exception is when a surfactant was used or when (MWCNTs) was involved. For such cases, the surface tension decreases compared to the pure base fluid. The hypothesis is the polymer groups attached to (MWCNTs) and the surfactant layer between a particle and the surround fluid increases the electrostatic force between particles and thus reduce surface energy and surface tension.