Analysis of structure–properties relationship in nitrile‐butadiene rubber/phenolic resin/organoclay ternary nanocomposites using simple model system

The present study deals with the structure–property relationship of organoclay (OC) filled nanocomposites based on rubber blend comprising of nitrile‐butadiene rubber (NBR) and phenolic resin (PH). To obtain a better insight into the characteristics of the NBR/PH/OC hybrid system, a simple model system consisting of NBR/OC nanocomposites is also taken into consideration. A series of NBR/OC and NBR/PH/OC nanocomposites containing a wide range of OC concentrations (2.5–30 phr) are prepared by using traditional open two‐roll mill. Structural analysis performed by X‐ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM) exhibits mixed exfoliated and intercalated morphology at low OC content, below 7.5 phr, and a well‐ordered intercalated morphology at higher OC loading. It is shown that the dispersion of OC is also influenced by mixing time and order of mixing of components. Analysis of the cure characteristics, mechanical, and thermal properties of both the NBR/OC and NBR/PH/OC nanocomposites reveals that the OC is dispersed mainly in the NBR continuous phase, even though some is likely localized in the rubber–resin interface. Copyright © 2009 John Wiley & Sons, Ltd.     

A comprehensive study on the impact of RGO/MWCNT hybrid filler reinforced polychloroprene rubber multifunctional nanocomposites

Flexible dielectric chloroprene rubber (CR) nanocomposites reinforced by one-dimensional carbon nanotube (CNT)/two dimensional reduced graphene oxide hybrids have been prepared using two-roll mill mixing technique. Non-covalent π-π interaction between multiwalled carbon nanotubes (MWCNTs) and reduced graphene oxide (RGO) nanosheets and the secondary interaction between fillers and chloroprene rubber matrix are responsible for generating the effective load transfer between RGO/MWCNTs and CR. The prepared RGO-MWCNT hybrid nanocomposites with high dielectric constant (≈650), low dielectric loss (≈0.42) and high energy storage efficiency (78.6%) values are practically good enough to use as a low cost polymeric dielectric layer in transistors. Furthermore, the prepared nanocomposites showed excellent electromagnetic effectiveness; a maximum shielding efficiency of 11.87 dB @ 3.5 GHz was achieved at 4 phr of MWCNT loading. This excellent electromechanical performance can be ascribed to the synergistic effect of RGO-MWCNT hybrid suggesting that this novel hybrid nanocomposite serves as an attractive candidate in modern electronics and electric power systems.     

Synthesis and characterization of graphene‐containing thermoresponsive nanocomposite hydrogels of poly(N‐vinylcaprolactam) prepared by frontal polymerization

Thermoresponsive poly(N‐vinylcaprolactam) nanocomposite hydrogels containing graphene were successfully prepared by frontal polymerization. High concentration of graphene (5.0 mg/mL) was obtained by direct graphite sonication in the self‐same liquid monomer, thus avoiding any chemical manipulation and obtaining “real” graphene as nanofiller instead of one of its more or less oxidized derivative, which is what generally reported in published reports. Furthermore, the corresponding nanocomposites were obtained without using any solvent to be eventually removed. The materials were fully characterized by RAMAN, SEM, and TEM, and their swelling behavior and rheological properties were investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Carbon nanotube‐filled ethylene/vinylacetate copolymers: from in situ catalyzed polymerization to high‐performance electro‐conductive nanocomposites

Preparation and analysis of morphology, mechanical, and electrical properties of nanocomposites based on ethylene vinyl acetate (EVA) copolymer and commercial multiwalled carbon nanotubes (CNTs) was achieved. The used techniques for obtaining nanocomposites were the conventional melt‐mixing and the in situ ethylene polymerization/coating reaction, as catalyzed directly from CNT surface, with different polyethylene content (i.e. 55.0% and 66.6%). Nanocomposites were also prepared using crude CNTs. The incorporation in the molten state of such polyethylene surface‐coated CNTs, used as “masterbatch,” in EVA was demonstrated a good strategy for allowing the complete destructuring of the native bundle‐like aggregates, leading to the preparation of polymer nanocomposites with largely improved properties, even at very low nanofiller content. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of modified graphene and microwave irradiation on the mechanical and thermal properties of poly(styrene‐co‐methyl methacrylate)/graphene nanocomposites

The effect of modified graphene (MG) and microwave irradiation on the interaction between graphene (G) and poly(styrene‐co‐methyl meth acrylate) [P(S‐co‐MMA)] polymer matrix has been studied in this article. Modification of graphene was performed using nitric acid. P(S‐co‐MMA) polymer was blended via melt blending with pristine and MG. The resultant nanocomposites were irradiated under microwave at three different time intervals (5, 10, and 20 min). Compared to pristine graphene, MG showed improved interaction with P(S‐co‐MMA) polymer (P) after melt mixing and microwave irradiation. The mechanism of improved dispersion and interaction of modified graphene with P(S‐co‐MMA) polymer matrix during melt mixing and microwave irradiation is due to the presence of oxygen functionalities on the surface of MG as confirmed from Fourier transform infrared spectroscopy. The formation of defects on modified graphene and free radicals on P(S‐co‐MMA) polymer chains after irradiation as explained by Raman spectroscopy and X‐Ray diffraction studies. The nanocomposites with 0.1 wt% G and MG have shown a 26% and 38% increase in storage modulus. After irradiation (10 min), the storage modulus further improved to 11.9% and 27.6% of nanocomposites. The glass transition temperature of nanocomposites also improved considerably after melt mixing and microwave irradiation (but only for polymer MG nanocomposite). However, at higher irradiation time (20 min), degradation of polymer nanocomposites occurred. State of creation of crosslink network after 10 min of irradiation and degradation after 20 min of irradiation of nanocomposites was confirmed from SEM studies. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation and properties of isobutylene–isoprene rubber–clay nanocomposites

Isobutylene isoprene rubber (IIR)‐clay nanocomposites have been prepared successfully by melt intercalation with maleic anhydride‐grafted IIR (Ma‐g‐IIR) and organophilic clay. In IIR‐clay nanocomposites, the silicate layers of the clay were exfoliated and dispersed into the monolayer. The nanocomposites exhibited greater gas barrier properties compared with those of Ma‐g‐IIR. When 15 phr clay was added, gas barrier properties were 2.5 times greater than those of Ma‐g‐IIR. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1182–1188, 2006     

Cure characteristics and properties of NBR composites filled with co‐precipitates of black liquor and montmorillonite

Acrylonitrile‐butadiene rubber (NBR) composites filled with co‐precipitates of black liquor and montmorillonite (CLM) were prepared by mechanical mixing on a two‐roll mill. The cure characteristics, mechanical properties, thermal properties, and thermo‐oxidative aging properties of NBR/CLM composites were evaluated. Scanning electron microscopy and transmission electron microscopy showed that the filler particles were well dispersed in the NBR/CLM composites. The scorch time and optimum cure time increase with increasing filler loading. A remarkable enhancement in tensile strength, elongation at break, 300% modulus, and shore “A” hardness was also observed. When the loading of CLM was 40 parts per hundred rubbers, it showed about seven times increase in tensile strength, about 1.8 times increase in elongation at break, about three times increase in 300% modulus, and about 1.3 times increase in shore A hardness, respectively, as compared with those of pure cured NBR. Thermal properties and thermal oxidative aging properties, in general, were also improved with loading of this novel filler. Copyright © 2011 John Wiley & Sons, Ltd.     

Co‐continuous Polyamide 6 (PA6)/Acrylonitrile‐Butadiene‐Styrene (ABS) Nanocomposites

Summary: Polyamide 6 (PA6)/acrylonitrile‐butadiene‐styrene (ABS) (40/60 w/w) nanocomposites with a novel morphology were prepared by the melt mixing of PA6, ABS and organoclay. The blend nanocomposites had a co‐continuous structure, in which both PA6 and styrene‐acrylonitrile (SAN) were continuous phases. It was found that the toughening rubber particles were only located in the SAN phase and the strengthening clay platelets were selectively dispersed in the PA6 phase. The co‐continuous nanocomposites showed greatly improved mechanical properties over the whole temperature range when compared with the same blend sample without clay.

Schematic diagram for the co‐continuous ABS/PA6 blend nanocomposite.     

Stimuli‐responsive polymer nanocomposites based on styrene‐butadiene rubber and bacterial cellulose whiskers

Water‐induced mechanically adaptive rubber nanocomposites were prepared by mixing bacterial cellulose whiskers (BCWs) suspension with styrene‐butadiene rubber (SBR) latex, followed by evaporation method. The structure, morphology, dynamic mechanical properties, water stimuli‐responsive behavior, and biodegradability of SBR/BCWs nanocomposite films were investigated. The results showed that the hydrophilic whiskers had a significant reinforcement effect on the storage modulus of SBR matrix, which originated from the formation of a rigid three‐dimensional filler network within matrix by strong hydrogen bonding between whiskers. The SBR/BCWs nanocomposites showed pronounced water stimuli‐responsive behavior compared with neat SBR. The storage modulus of SBR/BCWs nanocomposite could be decreased by 99.2% after equilibrium water swelling. This remarkable water‐triggered modulus change is attributed to the disentanglement of BCWs network via competitive hydrogen bonding with water.     

Influence of organoclay dispersed state of poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate)/organoclay nanocomposites on their characteristics

This work prepared poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate) (PETG)/organoclay nanocomposites via a melt intercalation process and investigated the influences of organoclay aspect ratio and organoclay content on the dispersed state, mechanical, thermal, gas barrier, and heat recovery properties of PETG/organoclay nanocomposites. X‐ray diffraction (XRD) and transmission electron microscopic analyses showed that the organoclay dispersed in the polymer matrix with intercalation in the nanometer scale range. Differential scanning calorimetry (DSC) analysis demonstrated that all of the obtained nanocomposites were amorphous, indicating that the addition of organoclay did not affect the amorphous nature of PETG. The gas barrier properties of the nanocomposites improved with organoclay content and the properties were also affected by the organoclay aspect ratio. Water vapor and oxygen transmission rates (OTRs) of PETG/organoclay nanocomposites containing 3 phr Cloisite 15A, and 3 phr modified polymer grade Na‐montmorillonites (MPGN) were the lowest among the samples tested, and were 41.7 and 44.3%, respectively, of those of neat PETG. Similar organoclay content‐ and aspect ratio‐related effects were observed in the mechanical and heat recovery properties of the tested nanocomposites. Copyright © 2010 John Wiley & Sons, Ltd.     

Brominated poly(isobutylene‐co‐para‐methylstyrene) (BIMS)‐clay nanocomposites: Synthesis and characterization

In this work, preparation and properties of different nanoclays modified by organic amines (octadecyl amine, a primary amine, and hexadecyltrimethylammonium bromide, a tertiary amine) and brominated polyisobutylene‐co‐paramethylstyrene (BIMS)‐clay nanocomposites are reported. The clays and the rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray diffraction peaks observed in the range of 3 °–10 ° for the modified clays disappear in the rubber nanocomposites. TEM photographs show predominantly exfoliation of the clays in the range of 12 ± 4 nm in the BIMS. In the FTIR spectra of the nanocomposites, there are common peaks of virgin rubber as well as those of the clays. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus is observed on incorporation of the nanoclays in the BIMS. Structure‐property correlation in the above nanocomposites is attempted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4489–4502, 2004     

Uncross‐linked polypropylene (PP)/ethylene‐propylene‐diene (EPDM)/multi walled carbon nanotube (MWCNT) and dynamically vulcanized PP/EPDM/MWCNT nanocomposites

In this study, relatively large amounts of polypropylene (PP), ethylene‐propylene‐diene (EPDM), and multi‐walled carbon nanotube (MWCNT) were melt‐mixed with and without DCP. Dynamically vulcanized PP/EPDM (TPV)/MWCNT nanocomposites were prepared by two methods: the MWCNTs were added either before or after the dynamic vulcanization of the blends. The effects of composition, rotor speed, and dynamic vulcanization on their surface resistivity were investigated. The surface resistivity of uncross‐linked PP/EPDM/MWCNT nanocomposites increases with increasing the content of EPDM. At PP/EPDM (70/30 wt%) nanocomposite with 1.5 phr MWCNT, slightly lower surface resistivity is obtained by increasing the rotor speed during mixing. However, for PP/EPDM (50/50 wt%) and PP/EPDM (30/70 wt%) nanocomposites, surface resistivity decreases with increasing the rotor speed from 30 to 60 rpm. But further increase in rotor speed (90 rpm) leads to an increase of surface resistivity. When the MWCNTs were added after the dynamic vulcanization of the blends, the surface resistivity of TPV70/MWCNTnanocomposite is lower than that of uncross‐linked PP/EPDM/MWCNT nanocomposite. However, when the MWCNTs were added before the dynamic vulcanization of the blends, the surface resistivity of TPV70/MWCNT nanocomposite is >10¹² Ω/square. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation of high damping elastomer with broad temperature and frequency ranges based on ternary rubber blends

Based on the blends of chlorinated butyl rubber (CIIR), nitrile butadiene rubber (NBR) and chloroprene rubber (CR), a kind of high damping elastomer with broad temperature and frequency ranges is prepared. CIIR/NBR binary blend is prepared to take advantage of the immiscibility and the large difference in cross‐link density of the different phases caused by the curatives and accelerators migration. The dynamic mechanical analysis reveals that the binary blend was immiscible and its loss factor (tanδ) versus temperature curves show two separated and expanded loss peaks when compared with those of pure cured CIIR and NBR. In order to improve its damping properties at room temperature, the third component CR with the polarity between CIIR and NBR was blended into the binary blend. The resulted CIIR/NBR/CR ternary blend has gained effective damping properties (tanδ > 0.3) in the temperature range of ?86.4 to 74.6°C and the frequency range of 10^?2 to more than 10⁹ Hz. Other effects on the damping properties of the ternary rubber were also studied. Copyright © 2013 John Wiley & Sons, Ltd.     

Direct Creation of Highly Conductive Laser‐Induced Graphene Nanocomposites from Polymer Blends

The current state‐of‐the‐art mixing strategies of nanoparticles with insulating polymeric components have only partially utilized the unique electrical conductivity of graphene in nanocomposite systems. Herein, this paper reports a nonmixing method of direct creation of polymer/graphene nanocomposites from polymer blends via laser irradiation. Polycarbonate‐laser‐induced graphene (PC‐LIG) nanocomposite is produced from a PC/polyetherimide (PC/PEI) blend after exposure to commercially available laser scribing with a power of ≈6 W and a speed of ≈2 cm s⁻¹. Extremely high electrical conductivities are obtained for the PC‐LIG nanocomposites, ranging from 26 to 400 S m⁻¹, depending on the vol% of the starting PEI phase in the blend. To the authors' knowledge, these conductivity values are at least one order of magnitude higher than the values that are previously reported for conductive polymer/graphene nanocomposites prepared via mixing strategies. The comprehensive microscopy and spectroscopy characterizations reveal a complete graphitization of the PEI phase with columnar microstructure embedded in the PC phase.     

Nanotailoring of sepiolite clay with poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene]: structure–property correlation

Poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS)/sepiolite clay nanocomposites are prepared by solvent casting method. Two types of schemes have been adopted to establish the compatibility between nonpolar polymer (SEBS) and needle‐like inorganic filler (sepiolite), either by polar modification of the nonpolar polymer or organic modification of the inorganic filler. Structure–property correlation of nanocomposites derived from two different approaches is compared. Structural and morphological analysis of nanocomposites has been investigated by Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. Fourier transform infrared result shows better compatibility between SEBS and modified sepiolite clay compared to maleic anhydride grafted SEBS and pristine sepiolite in their nanocomposites. Tensile strength and % elongation are found to increase by 32 and 105%, respectively, with the addition of just 3 parts per hundred parts of resin (phr) modified sepiolite clay to pristine SEBS matrix. Moreover, thermal stability has also improved by 96°C with similar loading. This work provides a new insight into the structure and thermo‐mechanical properties of novel SEBS–sepiolite clay nanocomposites. Copyright © 2017 John Wiley & Sons, Ltd.     

Processable and Robust MoS2 Paper Chemically Cross‐Linked with Polymeric Ligands by the Coordination of Divalent Metal Ions

Inorganic graphene analogues (IGAs) are a huge and fascinating family of compounds that have extraordinary electronic, mechanical, and thermal properties. However, one of the largest problems that face the industrial application of IGAs is their poor processability, which has led to a “bottlenecking” in the development of freestanding, large‐area, IGA‐based thin‐film devices. Herein, we report a facile and cost‐efficient method to chemically modify IGAs by using their abundant coordination atoms (S, O, and N). Taking MoS₂ as an example, we have prepared homogeneous “solution” systems, in which MoS₂ nanosheets are chemically cross‐linked through a carboxylate‐containing polymeric ligand, poly(methyl methacrylate) (PMMA), by copper‐ion coordination. Bonding interactions between C?O bonds and sulfur atoms through copper ions were confirmed by various characterization techniques, such as UV/Vis, FTIR, and Raman spectroscopy and XPS. By using our method, freestanding MoS₂ paper with significantly improved mechanical properties was obtained, thus laying the basis for the mass production of large‐area MoS₂‐based thin‐film devices. Furthermore, copper‐ion coordination was also applied to MoS₂/PMMA nanocomposites. Direct and strong nanofiller/matrix bonding interactions facilitate efficient load transfer and endow the polymeric nanocomposites with an excellent reinforcement effect. This method may pave a new way to high‐strength polymeric nanocomposites with superior frictional properties, flame retardance, and oxidation resistance.     

甲基丙烯酸镁增强氢化丁腈橡胶的结构与形态和性能

用不同份量的甲基丙烯酸镁(MgMA)作增强剂,过氧化二异丙苯(DCP)作硫化剂,通过混炼和硫化过程的原位聚合制备了氢化丁腈橡胶/聚甲基丙烯酸镁(HNBR/PMgMA)纳米复合材料,用XRD、FTIR1、3C-NMR、SEM、TEM、DMA和交联密度分析等方法研究了其结构、形态和性能,并阐述了MgMA改性HNBR的相关机理.结果表明,MgMA在混炼过程中粒径明显变小,部分达到纳米级.硫化过程中发生原位自由基聚合,并部分接枝到HNBR分子链上,HNBR硫化胶和PMgMA有可能形成接枝互穿聚合物网络(接枝IPN).随着MgMA用量的增加,纳米复合材料硫化胶的定伸应力、拉伸强度、扯断伸长率、撕裂强度和热氧老化性能逐渐提高.当MgMA含量为30份时,体系的拉伸强度和扯断伸长率分别为38.5MPa和545%,并具有优异的热空气老化性能.MgMA能明显增加HNBR复合材料的储能模量,并降低其损耗因子.随着MgMA用量的增加,纳米复合材料硫化胶的总交联密度(Ve)和离子键交联密度(Ve2)增加,而共价键交联密度(Ve1)下降,表明离子键对HNBR/PMgMA纳米复合材料的力学性能起重要作用.     

Structure and properties of natural rubber/butadiene rubber (NR/BR) blend/sodium-montmorillonite nanocomposites prepared via a combined latex/melt intercalation method

75/25 (wt %) NR/BR blend/clay nanocomposites were prepared via a combined latex/melt intercalation method, for the first time. At first, NR latex was mixed with various amounts of the aqueous sodium montmorillomte (Na-MMT) dispersion. Obtained mixtures were co-coagulated by dilute solution of the sulfuric acid, washed several times with the distilled water and dried under vacuum. The NR/ clay compounds were then mixed with given amounts of the BR and vulcanizing ingredients in a 6-inch two-roll mill and then vulcanized at 150°C in a hot press. The nanocomposites have better mechanical properties than the clay-free NR/BR blend vulcanizates. Furthermore, modulus and hardness (Shore A) increased by increase of the clay loading in the range of 0–15 phr while tensile strength and elongation at break increased with increasing the clay content up to 5 phr and then decreased gradually by further increase of the clay loading. It was concluded from results of the XRD and mechanical test that nanocomposites containing less than 10 phr clay may show the fully exfoliated structure. With increasing the clay content to 10 and 15 phr, both non-exfoliated (stacked layers) and exfoliated structures may be observed simultaneously in the nanocomposites. TGA results indicated an improvement in main and end decomposition by increasing the clay loading.     

Click coupled graphene for fabrication of high‐performance polymer nanocomposites

An effective technique of using click coupled graphene to obtain high‐performance polymer nanocomposites is presented. Poly(ε‐caprolactone) (PCL)‐click coupled graphene sheet (GS) reinforcing fillers are synthesized by the covalent functionalization of graphene oxide with PCL, and subsequently the PCL‐GS as a reinforcing filler was incorporated into a shape memory polyurethane matrix by solution casting. The PCL‐click coupled GS has shown excellent interaction with the polyurethane matrix, and as a consequence, the mechanical properties, thermal stability, thermal conductivity, and thermo‐responsive shape memory properties of the resulting nanocomposite films could be enhanced remarkably. In particular, for polyurethane nanocomposites incorporated with 2% PCL‐GS, the breaking stress, Young's modulus, elongation‐at‐break, and thermal stability have been improved by 109%, 158%, 28%, and 71 °C, respectively. This click coupling protocol offers the possibility to fully combine the extraordinary performance of GSs with the properties of polyurethane. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Structure and properties of NR/BR blend/clay nanocomposites prepared by the latex method

Rubber blend/clay nanocomposites based on the 50/50 (wt %) natural rubber/butadiene rubber was prepared by the latex method via mixing the latex of 50/50 NR/BR blend with different amounts of the aqueous sodium montmorillonite (Na-MMT) dispersion and co-coagulating the mixture. XRD and TEM were used to characterize structure of the nanocomposites. It was found that fully exfoliated structure could be obtained by this method only when the low loading of layered silicate (up to 5 phr) is used. With increasing the clay content, both non-exfoliated (stacked layers) and exfoliated structures can be observed simultaneously in the nanocomposites. Nanocomposites showed mechanical properties better than the clay-free volcanizate. Moreover, modulus, tensile strength, elongation at break and tear strength increased significantly by increasing the clay amount up to 5 phr and then remained almost constant by further increasing the clay content. Improvement in the mechanical properties by increasing the clay loading up to 5 phr was attributed to the nano-reinforcement effect of Na-MMT. TGA results indicated an improvement in the main decomposition temperature by increasing the clay amount.