Surface‐activated nanosilica treated with silane coupling agents/polypropylene composites: Mechanical,morphological, and thermal studies

This work reports the mechanical, morphological, and thermal properties of the polypropylene (PP) nanocomposites containing nanosilica (nano‐SiO₂) which were treated by different functional group silane coupling agents. Four types of silane coupling agents namely aminopropyltriethoxy silane (APTES), glycidyloxypropyltrimethoxy silane (GPTMS), trimethoxysilylpropyl methacrylate (TMPM), and dichlorodimethyl silane (DCMS) were used to modify the surface‐activated nanosilica. To enhance the effectiveness of the coupling, nanosilica was chemically activated and analyzed through FTIR and X‐ray photo electron spectroscopy (XPS). The highest tensile strength was recorded by the activated nanocomposites treated with APTES followed by nanocomposite treated with GPTMS, TMPM, and DCMS, respectively. The addition of silane coupling agents into nano‐SiO₂/PP system further improved the tensile modulus of the PP nanocomposites. From the transmission electron microscopy (TEM) analysis, activated nanosilica treated with APTES showed better nanosilica dispersion in the PP matrix and lesser agglomeration occurred when compared with the other silane coupling agents which were used in this study. Surface activation process does not effectively increase the degree of crystallinity and thermal stability on the PP nanocomposites. However, with the assistance of the surface treatment, it was found that the thermal behavior of the PP nanocomposites had been enhanced. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Effect of the grafted silane on the dispersion and orientation of clay in polyethylene nanocomposites

The CTAB ammonium intercalated montmorillonite clay, CMT, was modified by an alkylsilane, Dodecyltrimethoxylsilane, to improve the miscibility of organoclays with PE matrix, involving the grafting reaction between the silane and silanol groups on the edge of clay. The silane modified clays (DMT) exhibited improved thermal stability due to the replacement of the physically adsorbed ammonium by the covalently bonded silane. The clays were melt compounded with polyethylene. Compared with the composite of PE/CMT, the clay dispersion state was improved, and a unique orientation of the clay layered was observed in PE/DMT nanocomposites, which was confirmed by XRD and TEM studies. The dispersion state, orientation degree of clay and, as a result, the mechanical and thermal properties of the nanocomposites were enhanced with the increasing amount of the grafted silane, indicating that the edge grafting of silane played a crucial role in controlling the structure and properties of nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

硅烷偶联剂原位改性白炭黑填充氢化丁腈橡胶（HNBR）复合材料性能研究

研究对比了硅烷偶联剂常温处理和原位改性白炭黑填充HNBR胶料性能,并进一步探索了不同种类的硅烷偶联剂原位改性白炭黑对HNBR复合材料性能的影响。结果表明,硅烷偶联剂原位改性白炭黑填充HNBR胶料的门尼粘度低、拉伸强度高、分散效果好和压缩永久变形小。使用硅烷偶联剂A151原位改性的HNBR胶料的门尼粘度较低,压缩永久变形最小。     

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     

The viscoelastic properties of modified thermoplastic impregnated multiaxial aramid fabrics

This study reports the manufacture of new fabric forms from the preparation of hybrid laminated multiaxial composites with enhanced thermo‐mechanical properties. Thermal and dynamic mechanical analysis of polymer matrix films and fabricated hybrid composites were used to determine the optimal material composition and reinforcement content for composites with improved viscoelastic properties. The introduction of 5 wt% silica nanoparticles in a composite of p‐aramid–poly(vinyl butyral) led to significant improvements in the mechanical properties, and the addition of silane coupling agents yielded maximal values of the storage modulus for hybrid nanocomposites. The introduction of silane led to a better dispersion and deagglomeration of SiO₂ particles, and to the formation of chemical bonds between organic and inorganic constituents, or p‐aramid–poly(vinyl butyral) composites. In this way, the mobility of macromolecules was reduced, which can be seen from the decreasing value of damping factor for the p‐aramid–poly(vinyl butyral) composite. Analysis of the glass transition temperature of the composite with amino‐functionalized silica nanoparticles revealed improved thermal stability in addition to the aforementioned mechanical properties of the tested materials. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Polystyrene nanocomposite materials: Preparation,morphology, and mechanical,electrical, and thermal properties

In this study, we prepared polystyrene (PS) resin nanocomposites with antistatic properties by melt‐blending PS with nanoscale zinc oxide (ZnO). The effects of nanoscale ZnO on the electrical and physical characteristics of the PS nanocomposites were investigated. Two kinds of nanoscale powders, spherical zinc oxide (s‐ZnO) and zinc oxide whisker (w‐ZnO), were selected. The coupling agents vinyltriethoxysilane (VTES) and phenyltriethoxysilane (PTES) were used to improve the compatibility between the nanopowders and PS resin. The addition of s‐ZnO and w‐ZnO improved the antistatic characteristics of the materials. The surface resistivities of the s‐ZnO and w‐ZnO nanocomposites were significantly reduced by modification with VTES and PTES. The addition of ZnO nanopowder increased the flexural modulus and reduced the flexural strength. The silane coupling agents improved the flexural properties of the nanocomposites. The glass‐transition temperatures and thermal degradation temperatures of the ZnO/PS nanocomposites increased with ZnO content. Treatment with silane increased the glass‐transition temperatures and thermal degradation temperatures of the composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2266–2273, 2005     

氧化锌晶须表面改性及表征

采用湿法表面化学改性法，用硅烷和钛酸酯偶联剂对氧化锌晶须(ZnOw)进行了表面改性；考察了溶剂、pH值、温度及分散时间对硅烷类偶联剂改性效果的影响，采用活化指数、接触角以及傅立叶变换红外光谱对改性结果作了表征。同时将改性后的ZnOw填充到线性低密度聚乙烯(LLDPE)中，测试了复合材料的机械性能。实验结果表明，硅烷和钛酸酯偶联剂均能用于ZnOw的表面改性，其最佳改性条件不同，获得最佳改性效果的偶联剂用量也不同。经ND-42改性的ZnOw填充到LLDPE中，复合材料的弯曲强度大幅度提高。     

Reconsideration of the effects of a coupling agent in talcum-filled plastics

Structure and morphology of talcum-filled polyethylene (HDPE–talc) were studied to examine the nature of beneficial effects of commercial silane coupling agents. Effects of the additive on the structures of the blends with various talc contents were studied through differential scanning calorimetry (DSC) analyses. Mechanism of reinforcement by the flake-like filler were analyzed through both classical treatments and a percolation model. Results suggest that for the studied system, silane had changed properties of the filled plastics, mainly through enhancement in filler dispersion and modification of matrix morphology. Choice of silane as coupling agents was thus questioned for the filled polyolefins with relatively low cost-to-performance ratio. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1227–1236, 1998     

The effect of clay dispersion on the properties of LLDPE/LLDPE‐g‐MAH/montmorillonite nanocomposites

In this work, three coupling agents presenting different grafting contents and molecular weights were used to prepare linear low density polyethylene (LLDPE)/linear low density polyethylene grafted with maleic anhydride (LLDPE‐g‐MAH)/montmorillonite nanocomposites with various morphologies. The clay dispersion was analyzed at the micrometric level by scanning electron microscopy and at the nanometric level by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that coupling agents having intermediate molecular weights led to the highest exfoliation extents, whereas the coupling agent presenting the highest molecular weight led to a poor delamination of the clay platelets. The properties of the nanocomposites produced and of their LLDPE/LLDPE‐g‐MAH reference blends were analyzed. It was shown that the best improvements in mechanical and barrier properties are not necessarily achieved for the nanocomposites, exhibiting the highest exfoliation extents. The length of the tactoids also plays a crucial role on the macroscopic properties. In addition, a high level of delamination could result in a loss of reinforcement effect, due to the inherent flexibility of the individual clay platelets. Finally, the strength of the clay/polymer interface, which was evaluated through surface tension measurements, seems to play a significant role on the properties of the nanocomposites. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Maleated and non-maleated polyethylene-montmorillonite layered silicate blown films: creep, dispersion and crystallinity

Non-linear time dependent creep of polyethylene (PE) montmorillonite layered silicate (MLS) nanocomposites was investigated. PE grafted maleic anhydride (PE-g-MA) was used, as a coupling agent to improve the miscibility between PE and organically modified MLS. The creep and tensile response of maleated and non-maleated PE nanocomposites were determined. Tensile properties of maleated PE nanocomposites were higher than the non-maleated nanocomposites. Non-linearity in the creep response was modeled using the Burger model. A drop in the retardation time was observed for maleated PE nanocomposites. XRD, polarized optical microscopy and a differential scanning calorimeter (DSC) were used to probe crystallinity and clay dispersion in the films. The tensile and creep properties were related to dispersion due to presence of MLS. The deformation response of PE blended with PE-g-MA and each of these separately modified by MLS showed synergistic contributions of the constituents. The response was attributed to dispersion effects with marginal effects of crystallinity.     

Retention of thermal antioxidants in polyethylene by silane coupling agents. II. Concentration and induction time studies

Thermal antioxidants were incorporated into polyethylene as solutions in the silane coupling agent N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane. Substantial improvements in retained concentration and induction time were observed for commercial phenolic and amine-type antioxidants on prolonged oven aging in thin polyethylene films. As an alternative to solution formation, a stabilizer was bonded directly to silicon as the organic functional group in a silane coupling agent, resulting in improved dispersion and induction time. Improvements in antioxidant retention and induction time appear to correlate with compatibility of the silane–polyethylene system.     

Polyethylene/aluminum nanocomposites: Improvement of dielectric strength by nanoparticle surface modification

The effect of the surface modification with a silane coupling agent (octyl‐trimethoxysilane) of aluminum (Al) nanoparticles on the dielectric breakdown behaviors of polyethylene (PE)/Al nanocomposites was investigated in comparison of the influence of the improvement of the interfacial adhesion between Al nanoparticles and PE using a compatibilizer (maleic anhydride grafted polyethylene). It was found that when compared with the other modification approaches, the surface‐treated Al nanofiller with the silane coupling agent makes it possible for the PE/Al nanocomposites to still keep the relatively higher breakdown strength even in the higher Al loading level above 14 vol %, which can be understood in terms of the better interfacial adhesion between the surface‐treated particle dispersion and the matrix. The combined effects of the Al nanoparticles on the different factors which influence the dielectric breakdown processes in polymer matrix such as microstructure, conductivity, and crystallinity of the nanocomposites were discussed in detail. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nanocomposites‐based polyolefins as alternative to improve barrier properties

This work investigates the influence of some ammonium quaternary compounds as coupling agent in polyethylene/clay nanocomposites to improve the performance of polyethylene used as packaging barrier material. The 3 wt % of vermiculite used as a nanofiller was added to linear low‐density polyethylene (LLDPE) and to linear low‐density polyethylene grafted with maleic anhydride (LLDPE‐g‐MA). The analysis results revealed that the influence of both the clay exfoliation in a polymer matrix and the coupling agents on the barrier properties were significant. Among the coupling agents used, cetylpropyldimethylammonium chloride yielded the best result for vermiculite exfoliation. A reduction of up to 18% in the oxygen‐permeability coefficient was observed in the nanocompounds with exfoliated vermiculite. The nanocomposite produced with vermiculite did not prove to be efficient as a moisture barrier against according to the analysis performed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of polypropylene/org-attapulgite nanocomposites

Polypropylene (PP)/org-attapulgite (ATP) nanocomposites were prepared by melt blending in a mixer apparatus. Org-attapulgite was attained by silane coupling agent modification first and then graft-polymerization with butyl acrylate. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the clay morphology and the dispersion of the org-attapulgite, respectively. The changes of crystalline structure for PP nanocomposites were characterized by X-ray diffraction (XRD). The mechanical properties of PP/attapulgite nanocomposites were studied through tensile and impact tests. The thermal and dynamic mechanical properties were characterized by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The strength and stiffness of PP/org-ATP nanocomposites were both improved significantly in the presence of organic attapulgite. In addition, the incorporation of org-ATP also gave rise to an increase of the storage modulus and the changes of the glass transition temperature for PP composites. TEM and XRD results revealed the addition of attapulgite did not change the crystal structure of PP, however org-attapulgite acted as nucleating agents for the crystallization of PP.     

Polystyrene/attapulgite nanocomposites prepared via in situ suspension polymerization with redox initiation system

A series of polymer–clay nanocomposites consisting of polystyrene (PS) and attapuglite (ATP) were prepared successfully. First, silane coupling agent containing aromatic tertiary amine groups was synthesized to functionalize ATP (M‐ATP). Then, PS nanocomposites with varied clay loadings were prepared via in situ suspension polymerization process with a redox initiation system consisting of aromatic tertiary amine and benzoyl peroxide. The synthesis of silane coupling agent and functionalization of ATP were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectra, and X‐ray photoelectron spectroscopy. Mechanical properties, morphology, thermal stability, and rheological behavior of nanocomposites were investigated to illuminate the effects of M‐ATP on the structure and properties of nanocomposites. Field‐emission scanning electron microscope images revealed an ideal dispersion of M‐ATP and an enhanced toughness of nanocomposites. The improved interface interaction between M‐ATP and PS matrix endowed the nanocomposites with outstanding mechanical properties and thermal stability. The formation of hybrid network in the nanocomposites containing 3 wt % M‐ATP resulted in higher complex viscosity (η*), storage modulus (G′), and lower loss factor (tanδ) compared with the pristine PS and PS/ATP nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41567.     

Simultaneous improvement in strength,toughness, and thermal stability of epoxy/halloysite nanotubes composites by interfacial modification

This work investigated the effect of silane modification of halloysite nanotubes (HNTs) on the mechanical properties of epoxy/HNTs nanocomposites. Three kinds of silane coupling agents, including 3‐(2‐aminoethyl)‐aminopropyltrimethoxysilane (AEAPS), (3‐glycidyloxypropyl)‐trimethoxysilane (GPTMS), and octyltriethoxysilane (OTES), were employed. It was shown that the modified HNTs exhibited a better dispersion in the epoxy matrix compared with pristine one. Because of strong interfacial interaction between AEAPS modified HNTs and the epoxy matrix, the nanocomposites exhibited the highest glass transition temperature and modulus among all the samples. On the other hand, AEAPS and GPTMS modified HNTs/epoxy nanocomposites showed enhanced tensile strength and toughness. The toughing mechanisms were identified by the SEM micrographs of the fracture surfaces of the different kinds of samples. In this study, simultaneous enhancement of strength, toughness, and thermal stability of epoxy by the modified HNTs provides a novel approach to produce high‐performance thermosets. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43249.     

Effect of silane as surface modifier and coupling agent on rheological and protective performance of epoxy/nano-glassflake coating systems

Epoxy resin nanocomposites suspended with nano-glassflakes (NGFs) are studied in the present work. A bi-functional silane, i.e., epoxy propoxy propyl tri-methoxy silane, was used as coupling agent and NGFs’ surface modifier. Fourier transformed infrared spectroscopy and thermogravimetry techniques confirmed the successful surface treatment of the NGFs. Rheological studies of the polymer composites were carried out by measuring complex viscosity and storage and loss modulus values. The rheological results revealed that the presence of silane either as coupling agent or as surface modifier could decrease the nanocomposite viscosity. It is indicated that reduced filler–filler interaction resulted in better dispersion of NGFs. It can be due to soft layer formation on nano-glassflakes by silane groups which prevents the agglomeration of NGFs and subsequently improves their dispersion quality. Storage and loss modulus investigations showed that an inter-connected network structure in the solution might be formed in the presence of silane, probably due to the interaction between the NGFs and the polymer resin phase. Electrochemical impedance spectroscopies were carried out to study the protective performance of epoxy/nano-glassflakes coatings. Although the electrochemical impedance results revealed that the incorporation of silane as coupling agent and surface modifier in the epoxy/NGF coating systems applied on carbon steel substrates could improve the protective performance, the superiority of the epoxy coating formulated with 0.5 wt% of modified NGF was obviously visible during immersion period.     

The influences of silane coupling agents on rheological properties of bentonite/nitrile butadiene rubber nanocomposites during curing process

In the present work, the influences of different silane coupling agents (SCA) on the rheological behaviors of Bent/NBR nanocomposites during the curing process were investigated. The nanocomposites were prepared with a green method which is simple and free of organic solvents. The dispersion state and filler–polymer interfaces were analyzed with XRD, TEM, and SEM while rheological behaviors of the nanocomposites were explored with a rubber processing analyzer (RPA). (3‐Mercaptopropyl)trimethoxysilane (MPTMS) and bis[3‐(triethoxysilyl)propyl] tetrasulfide (TESPT) both improved the dispersion state of bentonite in the matrixes significantly. MPTMS increased the crosslinking density by forming single sulfur bonds while TESPT worked as a plasticizer and delayed the formation of crosslinking during curing process. [3‐(2‐Aminoethylamino)propyl]triethoxysilane (AEAPTMS) led to reversible filler–rubber interactions, which was the main reason for the low elastic torque of the vulcanized nanocomposites. J. VINYL ADDIT. TECHNOL., 25:236–242, 2019. © 2018 Society of Plastics Engineers     

Curing and barrier properties of NBR/organo-clay nanocomposite

Organo-montmorillonite/NBR nanocomposites were prepared by a melt intercalation process. The characteristics of NBR nanocomposites were characterized by oscillating-disk rheometer, water-vapour transmission and transmission electron microscopy (TEM). Changes in cure characteristics resulting from changes in clay content and the addition of silane coupling agent were investigated. The study confirmed that organo-montmorillonite/NBR nanocomposites cure characteristics, viz minimum torque, maximum torque, scorch time and curing time, change according to the change in clay content and the addition of silane coupling agent. Of the water-vapour transport properties, the clay content and silane content are the dominating factors in determining the individual water-vapour permeability of these NBR nanocomposites. TEM analysis provided clear evidence for the homogeneous dispersion of clay in the NBR matrix without regard to increases in clay content. Copyright © 2004 Society of Chemical Industry     

Structure and mechanical properties of nanodispersed fibrous silicate‐reinforced ethylene–propylene–diene monomer nanocomposites

In this study, ethylene–propylene–diene monomer (EPDM)/fibrillar silicate (FS) nanocomposites were successfully prepared by mechanically blending EPDM with FS, which was modified by silane coupling agent KH570 containing methacryloxy group. The effects of silane content and modified FS on the dispersion of FS and mechanical properties of the composites were investigated. The impact of water in FS on mechanical properties of the composites was also evaluated. The results showed that modified FS could be dissociated into nanofibers dispersing evenly in the EPDM matrix by increasing substantially the loading of silane through the mechanical blending. The optimum loading level of silane coupling agent was up to 24 phr/100 phr FS. Silane KH570 could improve the dispersion of FS and strengthen nanofibers–rubber interfacial adhesion even at the loading of as high as 50 phr FS, making FS to exhibit excellent reinforcement to EPDM. Too much FS could not be completely dissociated into nanofibers, slowing down further improvement. The EPDM/FS composites exhibited the similar stress–strain behavior and obvious mechanical anisotropy with short microfiber‐reinforced rubber composites. With the increase in silane coupling agent and modified FS, the number of nanofibers increased because of the exfoliation of FS microparticles; thus, the mechanical behaviors would become more obvious. It was suggested that the free water in FS should be removed before mechanically blending EPDM with FS because it obviously affected the tensile properties of the composites. Regardless of whether FS was dried or modified, the EPDM/FS composites changed little in tensile strength after soaked in hot water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011