Synthesis and exfoliation of bismaleimide–organoclay nanocomposites

Bismaleimide-clay nanocomposites were synthesized by swelling two kinds of organophilic clays (OCLs) in allyl-compound modified bismaleimide (BMI) resins and subsequent thermal curing and characterized by DSC, Wide-angle X-ray diffraction (WAXD), Field emission SEM, TEM and Rheometer. The results indicated that the synthesis of modified BMI-clay nanocomposites was determined by the factors including the preparation methodology, curing conditions, and nature of OCLs. Exfoliation of clay can be promoted by homogeniser and ultrasonication. Allyl-compound played a key role for the exfoliation of OCLs in modified BMI matrix as the pre-intercalation agent. It seems that the exfoliation should be carried out before gelation in order to obtain fully exfoliated structure in modified BMI matrix. The good combination of compatibility and acceleration effect on the intragallery polymerization are the favorable conditions to obtain exfoliated nanocomposites based on modified BMI matrix. The exfoliated structure favored the improvement in impact strength.     

Comparison of the influence of different compatibilizers on the structure and properties of ethylene vinyl acetate copolymer/modified clay nanocomposites

Nanocomposites of an ethylene vinyl acetate copolymer and clay were prepared by melt blending and extrusion. Two different compatibilizers, ethylene glycidyl methacrylate (EGMA) and maleic anhydride grafted polypropylene (MAPP), were used in these nanocomposites. The structural properties of the composites were characterized with X‐ray diffraction and transmission electron microscopy. The surface morphology was characterized with polarized optical microscopy. The tensile and permeability properties were studied. The thermal stability of the nanocomposites was characterized through thermogravimetric analysis. MAPP‐compatibilized nanocomposites had intercalated and partially exfoliated structures, whereas EGMA‐compatibilized nanocomposites had completely exfoliated structures. The EGMA‐compatibilized nanocomposites were thermally more stable than the MAPP‐compatibilized nanocomposites. The mechanical and permeability properties of the EGMA‐compatibilized nanocomposites were better than those of the MAPP‐compatibilized nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Possible mechanism of interaction among the components in MAPP modified layered silicate PP nanocomposites

Model reactions were carried out with components frequently used for the preparation of intercalated or exfoliated polypropylene (PP) nanocomposites. The results prove that maleinated polypropylene (MAPP) can react chemically with the surfactant applied for the organophilization of the filler, if this latter contains active hydrogen groups. The reaction of hexadecylamine (HDA) and MAPP was detected by MALDI-TOF spectroscopy, DSC measurements and FTIR spectroscopy. Anhydride groups are consumed and mainly amide groups form in the reaction. The formation of cyclic imides could not be proved by the techniques used. MAPP reacts also with the surfactant adsorbed on the surface of the silicate in ionic form. On the other hand, N-cetylpyridinium chloride (CPCl) not containing active hydrogen atoms does not react with maleinated PP. Intercalated or exfoliated composites could be prepared from the silicate organophilized with HDA, while microcomposites formed from the filler treated with CPCl. Chemical reactions remove the surfactant from the surface of MMT and hydrogenated silicate sites are left behind. The high energy surface interacts either with the anhydride or the amide groups by dipole-dipole interactions. Even the unmodified polypropylene chains may be attached much stronger to the surface by London dispersion forces than to the silicate covered with aliphatic chains. Although the effect of competitive adsorption (MAPP, HDA) and mutual solubility of the components (PP, MAPP, surfactant, reaction products) cannot be neglected, chemical reactions play a crucial role in structure formation in PP nanocomposites containing a functionalized polymer. Direct interaction of the silicate surface and the functionalized polymer as well as the formation of hydrogen bridges seem to play a lesser role, but the relative influence of processes may change with the type of surfactant, functionalized polymer, surface coverage and processing conditions.     

A study of global vs. local properties for maleic anhydride modified polypropylene nanocomposites

Nanoindentation of organomodified clay filled maleated polypropylene (MAPP) was investigated. The study aims to identify the relative increase in local stiffness in comparison to the increase in mechanical properties of the bulk in polypropylene-based nanocomposites. Such a study allows one to assess confined material property in addition to increased filler volume at the local scale. A mixture of highly intercalated and well exfoliated clay structures, when dispersed in MAPP matrix, was observed under transmission electron microscopy. The degree of exfoliation was found to increase with clay loading, which was attributed to the higher viscosity and mechanical shear forces during melt compounding. Instrumented indentation was performed on (1) clay aggregate supported by MAPP matrix, (2) clay-matrix boundary, and (3) the MAPP matrix. The clay aggregated region generally showed higher stiffness as compared to the matrix. And, the relative increase in indentation stiffness is substantially higher than the relative increase in tensile and compressive stiffnesses for clay reinforced systems. Polymer chain confinement and topological constraint appeared to be operative to enhance local stiffness in the clay aggregated region. Good correlation was, however, obtained between the change in macroscopic stiffness and the change in highly local indentation stiffness as a result of clay reinforcement.     

Morphology,deformation behavior and thermomechanical properties of polypropylene/maleic anhydride grafted polypropylene/layered silicate nanocomposites

Nanocomposites polypropylene (PP) with 3 and 7 wt % of clay were prepared by melt mixing. Four types of maleic anhydride grafted PP (MAPP) in broad range of MA groups content (0.3–4 wt %) and molecular weights (MW) were used as polar compatibilizers. The effect of the MAPP kind on both the clay dispersion and miscibility with PP was studied. The mixed intercalated/exfoliated morphologies of nanocomposites in the presence of all studied compatibilizers were revealed by XRD and TEM. The oligomer compatibilizer with 4 wt % of MA groups increases the intercalation ability of polymer into clay galleries but this one has limited miscibility with PP and worsens crystalline structure of polymer matrix. The MAPPs with 0.3–1.3% of MA are characterized by the lower intercalation ability but well cocrystallize with PP. Maximum reinforcing effect is attained using high MW MAPP with 0.6% MA and for nanocomposite with 7 wt % (3.8 vol %) of clay it averages almost 1.7 times relative to neat PP and 1.3 times relative to noncompatibilized composite. Dynamic storage moduli of nanocomposites compatibilized by MAPPs with 0.3–1.3% of MA containing 7 wt % of clay increase up to 1.4–1.5 around 30–75°C and over the whole temperature range remain higher compared with both neat PP and uncompatibilized composite. On the contrary, the oligomer MAPP with 4 wt % of MA groups decreases the thermal–mechanical stability of nanocomposite at high temperature compared with both PP and uncompatibilized composites. The study of nanocomposites flammability showed that creating complex composites containing both layered silicate and relatively small amount of magnesium hydroxide can be a successful approach to reduce the combustibility of PP‐based nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of Clay Types on the Mechanical,Dynamic Mechanical and Morphological Properties of Polypropylene Nanocomposites

In the present investigation Polypropylene–Maleic anhydride grafted polypropylene–organically modified MMT (PP-MAPP-OMMT) nanocomposites were prepared by melt mixing in a twin screw extruder followed by injection molding. The effect of clay chemistry and compatibilizer on the properties of the nanocomposites has been studied. Sodium montmorillonite has been organically modified using quaternary and alkyl amine intercalants. A comparative account with commercial quaternary ammonium modified clays i.e Cloisite 20A, Cloisite 15A and Cloisite 30B has been presented. Storage modulus of PP matrix also increased in the nanocomposites, indicating an increase in the stiffness of the matrix polymer with the addition of organically modified nanoclays. The morphology of the nanocomposites has been examined using wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Morphological findings revealed efficient dispersion of organically modified nanoclays within the PP matrix. MAPP compatibilized PP/Cloisite 15A nanocomposites displayed finely dispersed exfoliated nanomorphology as compared with other systems.     

Effect of organoclay on the properties of maleic‐anhydride grafted polypropylene and poly(methyl methacrylate) blend

Poly(methyl methacrylate)/polypropylene (PMMA/PP) and PMMA/maleic‐anhydride grafted PP (MAPP) blends and their blend nanocomposites containing 2 wt% organoclay (Cloisite 15A, denoted C15A), prepared by a melt mixer were studied. Both X‐ray diffraction (XRD) and transmission electron microscopy (TEM) revealed exfoliated polymer blend nanocomposites. Scanning electron microscopy (SEM) studies indicated a droplet dispersion morphology for all the blends while addition of C15A into PMMA/MAPP blend resulted to a co‐continuous morphology. In fact, rheological data and thermal properties indicated that the PMMA/MAPP/C15A nanocomposite showed a better homogeneous dispersion of silicate layers than PMMA/PP/C15A nanocomposite. A Cole–Cole plot and relaxation modulus indicated a solid‐like character for PMMA/MAPP and PMMA/MAPP/C15A, while a liquid‐like behavior was noticed for PMMA/PP and PMMA/PP/C15A. The effect of an organoclay on the dynamic mechanical properties of samples was investigated using dynamic mechanical analysis (DMA) which showed a significant enhancement on the storage modulus of the PMMA/MAPP/C15A as compared to PMMA/PP/C15A . POLYM. COMPOS., 38:431–440, 2017. © 2015 Society of Plastics Engineers     

Study on thermoplastic polyurethane/montmorillonite nanocomposites

The thermoplastic polyurethane/montmorillonite (TPU/MMT) nanocomposites were prepared by melt intercalation. The structure and property of the TPU/MMT nanocomposites were studied by XRD, TEM, TG, Molau test, and mechanical property measurement. The interlayer spacing between the MMT platelets in TPU/MMT nanocomposites blended for 10 and 15 min was the same. The silicate platelets were dispersed in TPU matrix on 5–15 nm scale for TPU/MMT nanocomposites. The interface interaction between the silicate layers and TPU matrix for TPU/MMT nanocomposites was strong. Compared to those of pure TPU, the tensile strength and tear strength of the TPU/MMT nanocomposites increased. The tensile strength and tear strength of the TPU/MMT nanocomposites decreased with increasing blending time because of the degradation of the TPU matrix. The thermal stability of the TPU/MMT nanocomposites was lower than that of the pure TPU in the first step, whereas in the second step, the TPU/MMT nanocomposites showed higher thermal stability. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Effect of Organo-Modified Montmorillonite on the Morphology and Properties of SEBS/TPU Nanocomposites

In this study, novel polystyrene-b-poly(ethylene-butylene)-b-polystyrene (SEBS)/thermoplastic polyurethane (TPU)/organo-modified montmorillonites (OMMT) nanocomposites were prepared by melt mixing. Three different organo-modified montmorillonites, DK2, DK3, and DK4 (listed in descending order of hydrophilicity) were selected. The compatibilizing and reinforcing effects of OMMT on the structure, morphology, thermal stability, mechanical and rheological properties of the SEBS/TPU blends were studied. It was found that the hydrophilic DK2 nanoparticles were largely located in the continuous TPU phase and partially dispersed at the phase interphase, whereas DK3 and DK4 nanoparticles were preferentially located at the phase interface with an intercalated/exfoliated and intercalated structure, respectively. Scanning electron microscopy (SEM) results showed that SEBS/TPU/OMMT nanocomposites exhibited a more densely organized and interconnected structure compared with SEBS/TPU blends. Better thermal property was achieved after adding DK3, with the tensile properties of the SEBS/TPU increased considerably. Rheological analysis revealed that hydrophilic DK2 nanoparticles were more effective in improving rheology properties and showed a more pronounced nonlinear effect. The prepared SEBS/TPU/OMMT nanocomposites displayed desired thermal, mechanical and rheological properties, which are important for many applications. POLYM. ENG. SCI., 60:850–859, 2020. © 2020 Society of Plastics Engineers     

Nanostructure morphology and dynamic rheological properties of nanocomposites based on thermoplastic polyurethane and organically modified montmorillonite

Thermoplastic polyurethane (TPU) nanocomposites based on organophilic-layered silicates were prepared via melt blending. Wide angle X-ray diffraction (WAXD) and transmission electron microscope (TEM) were employed to investigate the state and mechanism of exfoliation of the layered silicate within TPU matrix. The TPU nanocomposites were found to have a partially exfoliated morphology at lower clay loading, whereas the morphology changed to an intercalated nanostructure at higher clay loadings. The effect of the state of dispersion of organoclay on rheological properties of the nanocomposites were carried out by rubber process analyzer (RPA), which exhibited more pronounced shear thinning behavior, and increased storage and loss modulus with the increase in organoclay content. The pseudo-plastic like behavior was observed due to change in liquid-like to solid-like behavior of nanoclay-filled systems.     

Effect of sodium dodecylbenzene sulphonate modifier and PP-g-MA on the morphology and thermal conductivity of PP/EG composites

This study investigates the influence of expanded graphite (EG) and sodium dodecylbenzene sulfonate (SDBS) treated EG (SDBS/EG) on the structure, thermal stability and thermal conductivity of polypropylene (PP) and polypropylene/maleic anhydride-grafted polypropylene (PP/MAPP) blend. The dispersion of EG and SDBS/EG was characterized by scanning electron microscopy (SEM). The SDBS-EG showed a crushed and randomly deformed structure. There was an improved interfacial adhesion between the polymer and the SBDS-EG particles. The graphite dispersed much better with less restacking for PP/MAPP/SDBS/EG system. The better dispersion also contributed towards the improved compatibility between the PP or PP/MAPP and SBDS/EG. The SDBS functionalised EG composites showed better thermal stability than the non-functionalized SDBS composites. It was further shown that the functionalized graphite significantly improved the thermal conductivity of the PP and PP/MAPP. This is because the functionalized SDBS/EG seemed to improve the interfacial heat transfer between the conductive filler (EG) and PP matrix.     

Effect of modifiers on morphology and thermal properties of novel thermoplastic polyurethane‐peptized laponite nanocomposite

Laponite RDS (Laponite containing pyrophosphate based peptizer) was modified with cetyl trimethyl ammonium bromide (cLS) and dodecylamine hydrochloride (dLS), respectively. Thermoplastic polyurethane (TPU)‐modified Laponite RDS nanocomposites were prepared by solution mixing technique. Morphologies of these two modified clay‐nanocomposites are found to be markedly different. cLS based TPU nanocomposites exhibit partly exfoliated, intercalated, and aggregated structure at lower clay content but a network type of structure is observed at higher clay content. However, dLS based TPU nanocomposites demonstrate spherical cluster type of structure at all clay contents. Nearly two fold increase in storage modulus is observed in both glassy and rubbery state with merely 1% cLS content which gradually decreases with an increase in the clay content. However, in case of dLS filled nanocomposite, gradual increase in storage modulus is observed with an increase in the clay content. Thermogravimetric analysis (TGA) studies indicate that the temperature corresponding to 5 wt % degradation of TPU is enhanced by 19.1 and 12.5°C with the addition of merely 1% cLS and dLS, respectively. However, the activation energy of degradation of neat TPU, as determined by isothermal TGA analysis, is found to be higher than that of the nanocomposites containing 1% of cLS and dLS, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology and properties of thermoplastic polyurethane nanocomposites: Effect of organoclay structure

A series of alkyl ammonium/MMT organoclays were carefully selected to explore structure-property relationships for thermoplastic polyurethane (TPU) nanocomposites prepared by melt processing. Each organoclay was melt-blended with a medium-hardness, ester-based TPU, while a more limited number of organoclays was blended with a high-hardness, ether-based TPU. Wide-angle X-ray scattering, transmission electron microscopy, particle analysis, and stress-strain behavior were used to examine the effects of organoclay structure and TPU chemical structure on morphology and mechanical properties. Specifically, the following were observed: (a) one long alkyl tail on the ammonium ion rather than two, (b) hydroxy ethyl groups on the amine rather than methyl groups, and (c) a longer alkyl tail as opposed to a shorter one leads to higher clay dispersion and stiffness for medium-hardness TPU nanocomposites. Overall, the organoclay containing hydroxy ethyl functional groups produces the best dispersion of organoclay particles and the highest matrix reinforcement, while the one containing two alkyl tails produces the poorest. The two TPU's exhibit similar trends with regard to the effect of organoclay structure. The high-hardness TPU nanocomposites showed a slightly higher number of particles and clay dispersion. The organoclay structure trends are analogous to what has been observed for nylon 6-based nanocomposites; this suggests that polar polymers like polyamides, and apparently polyurethanes, have a relatively good affinity for the polar clay surface; and in the case of polyurethanes, the high affinity of the matrix for the hydroxy ethyl functional groups in the organoclay aids clay dispersion and exfoliation.     

Polypropylene reinforced with nanocrystalline cellulose: Coupling agent optimization

Five different grades of maleic anhydride polypropylene (MAPP) having different molecular weight and acid value (AV) were used as coupler in PP‐nanocrystalline cellulose (NCC) composites. The main objective was to study the effect of MAPP structure (Mw, AV) and filler/coupler (F/C) ratio on mechanical properties in order to find optimum mechanical properties in tension, flexion, and impact. Results showed that both Mw and AV have direct effect on mechanical properties and a balance between both must be achieved to get the best performance. However, regardless of MAPP structure, optimum improvement was obtained for F/C = 7.5/1. Shear rheological data showed that at high MAPP content, MAPP acts as lubricant. DSC and AFM analysis showed small reduction in the size of PP crystals in the presence of NCC. Rheological data under large amplitude oscillatory shear showed that the nanocomposites used here are under percolation. Using these analyses, possible reinforcement mechanisms were investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42438.     

Rheological behavior of polypropylene/layered silicate nanocomposites prepared by melt compounding in shear and elongational flows

Melt rheology and processability of exfoliated polypropylene (PP)/layered silicate nanocomposites were investigated. The nanocomposites were prepared by melt compounding process in the presence or absence of a PP‐based maleic anhydride compatibilizer. PP/layered silicate nanocomposites showed typical rheological properties of exfoliated nanocomposites such as nonterminal solid‐like plateau behavior at low frequency region in oscillatory shear flow, higher steady shear viscosity at low shear rate region, and outstanding strain hardening behavior in uniaxial elongational flow. The melt processability of exfoliated PP/layered silicate nanocomposites was significantly improved due to good dispersion of layered silicates and increased molecular interaction between the PP matrix and the layered silicate organoclay. Small‐angle X‐ray scattering and transmission electron microscopy results revealed that the layered silicate organoclay was exfoliated and good interaction between PP matrix and organoclay was achieved by using the PP‐g‐MAH compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3506–3515, 2007     

Preparation and physical properties of wood/polypropylene/clay nanocomposites

Wood plastic composites (WPCs) are attracting a lot of interests because they are economic, environmentally friendly, and show fairly good performance. To improve the performance of a wood/polypropylene (PP) composite, an organoclay was incorporated as a nanosize filler in this work. WPCs were prepared by melt blending followed by compression molding, and their performance was investigated by universal testing machine, izod impact tester, dynamic mechanical analyzer, thermal mechanical analyzer, differential scanning calorimetry, and TGA. Maleic anhydride polypropylene copolymer (MAPP) was used to increase compatibility between the PP matrix and wood particles and also improve the dispersion and exfoliation of the organoclay in the PP matrix. XRD analysis showed that the matrix of the WPCs with organoclay had intercalated structure. The SEM images of the WPCs with MAPP showed improved interfacial adhesion between the matrix and wood particles. The degree of water absorption increased with immersion time, but it could be restrained by incorporating MAPP. The performance of the WPCs was improved by the incorporation of the organoclay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of maleic anhydride‐g‐polypropylene/diamine‐modified clay nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by compounding maleic anhydride‐g‐polypropylene (MAPP) with MMT modified with α,ω‐diaminododecane. Structural characterization confirmed the formation of characteristic amide linkages and the intercalation of MAPP between the silicate layers. In particular, X‐ray diffraction patterns of the modified clay and MAPP/MMT composites showed 001 basal spacing enlargement as much as 1.49 nm. Thermogravimetric analysis revealed that the thermal decomposition of the composite took place at a slightly higher temperature than that of MAPP. The heat of fusion of the MAPP phase decreased, indicating that the crystallization of MAPP was suppressed by the clay layers. PP/MAPP/MMT composites showed a 20–35% higher tensile modulus and tensile strength compared to those corresponding to PP/MAPP. However, the elongation at break decreased drastically, even when the content of MMT was as low as 1.25–5 wt %. The relatively short chain length and loop structure of MAPP bound to the clay layers made the penetration of MAPP molecules into the PP homopolymer phase implausible and is thought to be responsible for the decreased elongation at break. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 307–311, 2005     

Kudzu fiber‐reinforced polypropylene composite

Kudzu fiber‐reinforced polypropylene composites were prepared, and their mechanical and thermal properties were determined. To enhance the adhesion between the kudzu fiber and the polypropylene matrix, maleic anhydride‐grafted polypropylene (MAPP) was used as a compatibilizer. A continuous improvement in both tensile modulus and tensile strength was observed up to a MAPP concentration of 35 wt %. Increases of 24 and 54% were obtained for tensile modulus and tensile strength, respectively. Scanning electron microscopy (SEM) showed improved dispersion and adhesion with MAPP. Fourier transform infrared (FTIR) spectroscopy showed an increase in hydrogen bonding with an increase in MAPP content. Differential scanning calorimetry (DSC) analysis indicated little change in the melting temperature of the composites with changes in MAPP content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1961–1969, 2002     

Preparation and characterization of thermoplastic polyurethane/organoclay nanocomposites by melt intercalation technique: Effect of nanoclay on morphology,mechanical, thermal,and rheological properties

Nanocomposites based on thermoplastic polyurethane (TPU) and organically modified montmorillonite (OMMT) were prepared by melt blending. Organically modified nanoclay was added to the TPU matrix in order to study the influence of the organoclay on nanophase morphology and materials properties. The interaction between TPU matrix and nanofiller was studied by infrared spectroscopy. Morphological characterization of the nanocomposites was carried out using X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy techniques. The results showed that melt mixing is an effective process for dispersing OMMT throughout the TPU matrix. Nanocomposites exhibit higher mechanical and thermal properties than pristine TPU. All these properties showed an increasing trend with the increase in OMMT content. Thermogravimetric analysis revealed that incorporation of organoclay enhances the thermal stability of nanocomposites significantly. Differential scanning calorimetry was used to measure the melting point and the glass transition temperature (T_g) of soft segments, which was found to shift toward higher temperature with the inclusion of organoclays. From dynamic mechanical thermal analysis, it is seen that addition of OMMT strongly influenced the storage and loss modulus of the TPU matrix. Dynamic viscoelastic properties of the nanocomposites were explored using rubber process analyzer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of carbon nanofiber reinforced thermoplastic polyurethane nanocomposites

The effect of CNFs on hard and soft segments of TPU matrix was evaluated using Fourier transform infrared (FTIR) spectroscope. The dispersion and distribution of the CNFs in the TPU matrix were investigated through wide angle X‐ray diffraction (WAXD), field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), polarizing optical microscope (POM), and atomic force microscope (AFM). The thermogravimetric analysis (TGA) showed that the inclusion of CNF improved the thermal stability of virgin TPU. The glass transition temperature (T_g), crystallization, and melting behaviors of the TPU matrix in the presence of dispersed CNF were observed by differential scanning calorimetry (DSC). The dynamic viscoelastic behavior of the nanocomposites was studied by dynamical mechanical thermal analysis (DMTA) and substantial improvement in storage modulus (E') was achieved with the addition of CNF to TPU matrix. The rheological behavior of TPU nanocomposites were tested by rubber processing analyzer (RPA) in dynamic frequency sweep and the storage modulus (G') of the nanocomposites was enhanced with increase in CNF loading. The dielectric properties of the nanocomposites exhibited significant improvement with incorporation of CNF. The TPU matrix exhibits remarkable improvement of mechanical properties with addition of CNF. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012