Influence of nano‐organomontmorillonite on the viscoelasticity of the poly(trimethylene terephthalate)/glass fiber/organomontmorillonite hybrid nanocomposites materials

The influences of organically modified montmorillonite (OMMT) on the viscoelasticity of poly(trimethylene terephthalate)/glass fiber/OMMT (PTT/GF/OMMT) hybrid nanocomposite materials at liquid, elastic and glassy states, respectively, were investigated by using the rotational rheometer and dynamic mechanical analyzer (DMA). The viscoelasticity results suggest that OMMT has many important influences on the structure, modulus and toughness of the hybrid nanocomposite materials. At melton state, the shear‐thinning phenomena of the hybrid composite melts become remarkable with increasing OMMT content. At low frequency, the shear storage modulus (G′) and shear loss modulus (G″) of the melts increase with increasing OMMT content. The melt's elastic response increases by OMMT, and OMMT improves the creep resistance of the melts; in addition, the stress relaxation of the hybrid composite melts become slow with increasing OMMT content, and the stress leavings becomes much higher with increasing OMMT content. At glassy state, the storage modulus of the hybrid nanocomposites increases with increasing OMMT content, while the materials' loss modulus increases first and then decreases with increasing OMMT content; therefore, OMMT nanosheets have reinforcement effect on the composites, and it also has definite toughening effect on the hybrid composite when the OMMT content is no >2 wt%. At rubbery state, the hybrid composites show lower decreasing storage modulus but have lower cold‐crystallization ability than that of pure PTT and PTT/GF composite. POLYM. COMPOS., 35:795–805, 2014. © 2013 Society of Plastics Engineers     

Crystallization behavior of biodegradable poly(L‐lactide)/multiwalled carbon nanotubes nanocomposites from the amorphous state

Crystallization behavior of biodegradable poly(L ‐lactide) (PLLA) and its nanocomposites at different carboxyl‐functionalized multiwalled carbon nanotubes (f‐MWNTs) contents from the amorphous state was studied in detail in this work. For the isothermal cold crystallization, the presence of f‐MWNTs enhances the isothermal cold crystallization of PLLA in the nanocomposites compared with that of neat PLLA at the same crystallization temperature; moreover, the overall cold crystallization rate of PLLA increases with increasing the f‐MWNTs content in the PLLA matrix while the crystallization mechanism does not change. For the nonisothermal crystallization, the f‐MWNTs also accelerate the crystallization process of PLLA. In addition, the activation energies of nonisothermal cold crystallization process were calculated using both the Kissinger and Friedman methods. The cold crystallization activation energies of PLLA are higher in the nanocomposites than in neat PLLA, indicating that the addition of f‐MWNTs into the PLLA matrix acts as a physical hindrance to retard crystallization. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Crystallization behavior of poly(p‐dioxanone)‐PU/montmorillonite nanocomposites prepared by chain‐extending reaction

Organo‐modified montmorillonites and poly(p‐dioxanone) (PPDO) diol prepolymers were used to prepare Poly(p‐dioxanone)‐PU/organic montmorillonite (PPDO‐PU/OMMT) nanocomposites by chain‐extending reaction. The crystallization behavior and spherulitic morphology of PPDO‐PU/OMMT nanocomposites were investigated by WXRD, differential scanning calorimetry, and polarized optical microscopy. The results show that the regularity of the chain structure plays a dominant role during the crystallization process rather than that of OMMT content and its dispersion status in PPDO matrix. With similar molecular weight and same OMMT content, PPDO‐PU/OMMT nanocomposite, which derived from lower molecular weight PPDO prepolymer, exhibits lower crystallization rate, melting point, and crystallinity. The influence of the clay content on the crystallization behavior highly depends on its dispersing state. The nucleating effect of OMMT can be only observed at high loading percentage. For the nanocomposites with low clay loading percentage, the retarding effect of exfoliated platelets on the chain‐ordering into crystal lamellae became the key factor. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of polymer matrix/montmorillonite compatibility on morphology and melt rheology of polypropylene nanocomposites

In this study, Ca²⁺‐montmorillonite (Ca²⁺‐MMT) and organo‐montmorillonite (OMMT) were modified by three compatibilizers with different degrees of polarity [poly(ethylene glycol) (PEG), alkyl‐PEG, and polypropylene (PP)‐g‐PEG]. PP/MMT nanocomposites were prepared by melt blending and characterized using X‐ray diffraction and transmission electron microscopy. The results showed the degree of dispersion of OMMT in the PP/PP‐g‐PEG/OMMT (PMOM) nanocomposite was considerably higher than those in the PP/PEG/OMMT and PP/alkyl‐PEG/OMMT nanocomposites, which indicated that the dispersion was relative to the compatibility between modified OMMT and PP matrix. Linear viscoelasticity of PP/MMT nanocomposites in melt states was investigated by small amplitude dynamic rheology measurements. With the addition of the modified MMT, the shear viscosities and storage modulus of all the PP/MMT nanocomposites decreased. It can be attributed to the plasticization effect of PEG segments in the three modifiers. This rheological behavior was different from most surfactant modified MMT nanocomposites which typically showed an increase in dynamic modulus and viscosity relative to the polymer matrix. The unusual rheological observations were explained in terms of the compatibility between the polymer matrix and MMT. In addition, the mechanical properties of PP/MMT nanocomposites were improved. A simultaneous increase in the tensile strength and toughness was observed in PP/PMOM nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Rheology of poly(propylene)/clay nanocomposites

The linear and nonlinear shear rheological behaviors of poly(propylene) (PP)/clay (organophilic‐montmorillonite) nanocomposites (PP/org‐MMT) were investigated by an ARES rheometer. The materials were prepared by melt intercalation with maleic anhydride functionalized PP as a compatibilizer. The storage moduli (G′), loss moduli (G″), and dynamic viscosities of polymer/clay nanocomposites (PPCNs) increase monotonically with org‐MMT content. The presence of org‐MMT leads to pseudo‐solid‐like behaviors and slower relaxation behaviors of PPCN melts. For all samples, the dependence of G′ and G″ on ω shows nonterminal behaviors. At lower frequency, the steady shear viscosities of PPCNs increase with org‐MMT content. However, the PPCN melts show a greater shear thinning tendency than pure PP melt because of the preferential orientation of the MMT layers. Therefore, PPCNs have higher moduli but better processibility compared with pure PP.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2427–2434,2004     

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

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

Preparation and structure and mechanical properties of poly(styrene‐b‐butadiene)/clay nanocomposites

Star‐shaped and linear block thermoplastic poly(styrene‐b‐butadiene) copolymer (SBS)/organophilic montmorillonite clays (OMMT) were prepared by a solution approach. The intercalation spacing in the nanocomposites and the degree of dispersion of nanocomposites were investigated by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The mechanical properties, dynamic mechanical properties, and thermal stability of these nanocomposites were determined. Results showed that SBS chains were well intercalated into the clay galleries and an intercalated nanocomposite was obtained. The mechanical strength of nanocomposites with the star‐shaped SBS/OMMT were significantly increased. The addition of OMMT also gave an increase of the elongation, the dynamic storage modulus, the dynamic loss modulus, and the thermal stability of nanocomposites. The increase of the elongation of nanocomposites indicates that SBS has retained good elasticity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3430–3434, 2004     

Crystallization,morphology, and mechanical properties of poly(butylene succinate)/poly(ethylene oxide)‐polyhedral oligomeric silsesquioxane nanocomposites

The biodegradable poly(butylene succinate) (PBS)/poly(ethylene oxide)‐polyhedral oligomeric silsesquioxane (PEO‐POSS) nanocomposites were prepared by the solution blending and melt‐injection methods. The effect of PEO‐POSS on the non‐isothermal and isothermal crystallization, morphology, as well as mechanical properties of PBS was carefully investigated. The PEO‐POSS nanoparticles dispersed well in the PBS matrix, with the diameters around 30 nm. From isothermal crystallization analysis, the incorporation of PEO‐POSS enhanced the crystallization of PBS due to the heterogeneous nucleation effect while the crystal structure of PBS remained. PBS/PEO‐POSS nanocomposites showed of higher glass transition temperatures than that of neat PBS, attributing to the existence of PEO‐POSS decreasing the flexibility of PBS chains. The elongation at break of the PBS/PEO‐POSS nanocomposites reached the maximum value with PEO‐POSS content of 5 wt%. However, the elastic modulus of PBS decreased after the incorporation of PEO‐POSS. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

Isothermal crystallization behavior of poly(L‐lactic acid)/organo‐montmorillonite nanocomposites

The isothermal crystallization behavior of poly(L ‐lactic acid)/organo‐montmorillonite nanocomposites (PLLA/OMMT) with different content of OMMT, using a kind of twice‐functionalized organoclay (TFC), prepared by melt intercalation process has been investigated by optical depolarizer. In isothermal crystallization from melt, the induction periods (t_i) and half times for overall PLLA crystallization (100°C ≤ T_c ≤ 120°C) were affected by the temperature and the content of TFC in nanocomposites. The kinetic of isothermal crystallization of PLLA/TFC nanocomposites was studied by Avrami theory. Also, polarized optical photomicrographs supplied a direct way to know the role of TFC in PLLA isothermal crystallization process. Wide angle X‐ray diffraction (WAXD) patterns showed the nanostructure of PLLA/TFC material, and the PLLA crystalline integrality was changed as the presence of TFC. Adding TFC led to the decrease of equilibrium melting point of nanocomposites, indicating that the layered structure of clay restricted the full formation of crystalline structure of polymer. The specific interaction between PLLA and TFC was characterized by the Flory‐Huggins interaction parameter (B), which was determined by the equilibrium melting point depression of nanocomposites. The final values of B showed that PLLA was more compatible with TFC than normal OMMT. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

The excellent gas barrier properties and unique mechanical properties of poly(propylene carbonate)/organo-montmorillonite nanocomposites

Intercalated nanocomposites comprised of poly(propylene carbonate) (PPC) and organo-montmorillonite (OMMT) were prepared via a direct melt blending method. The morphological, thermal, rheological, mechanical, and gas barrier properties of composites were carried out in detail. Results of XRD, TEM, and SEM revealed that OMMT dispersed homogeneously in the polymer matrix, and were intercalated by PPC macromolecules. Compared with neat PPC, the PPC/OMMT nanocomposites showed an enhancement in the 5 wt% weight loss temperature (T _?5%) by near 20 °C with 3 phr OMMT concentration. With the percolation threshold formed, the rheological properties of composites translated from a liquid-like behavior to a solid-like one. Interestingly, PPC/OMMT nanocomposites revealed a concurrent improvement in the modulus, yield strength, and toughness with the addition of homogeneously dispersed clay. The oxygen permeability of well-dispersed PPC/OMMT nanocomposites reduced significantly compared with that of neat PPC. Consequently, this convenient and effective method, which facilitates to prepare PPC/OMMT nanocomposites with superior mechanical properties and excellent gas barrier performances, can be considered to broaden the application of PPC.     

Preparation and characterization of microbial biodegradable poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)/organoclay nanocomposites

Novel biodegradable poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) [P(3HB‐co‐4HB)]/organoclay nanocomposites were prepared via solution casting. Exfoliated nanocomposite structure was confirmed by wide‐angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) for the nanocomposites with low organoclay loadings (≤3 wt%), whereas the mixtures of exfoliated and unexfoliated organoclays were appeared in the nanocomposite with an organoclay content of 5 wt%. The organoclay fillers accelerated significantly the cold crystallization process of P(3HB‐co‐4HB) matrix. The thermal stability of the nanocomposites was in general better than that of pristine P(3HB‐co‐4HB). Considerable increase in tensile modulus was observed for the nanocomposites, especially at an organoclay content of 3 wt%. These results demonstrated that the nanocomposites improved the material properties of P(3HB‐co‐4HB). POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Investigation of the rheological,dynamic mechanical,and tensile properties of single‐walled carbon nanotubes reinforced poly(vinyl chloride)

Polymer nanocomposites consisting of single‐walled carbon nanotubes (SWCNTs) and poly(vinyl chloride) were prepared by casting technique. The complex viscosity increased with increasing SWCNTs content, and it had a percolation concentration threshold equal to 0.45 wt % of SWCNTs. The storage modulus, G′, increased with increasing either SWCNTs content or frequency. A gradual decrease in the terminal zone slope of G′ for the nanocomposites with increasing SWCNTs content may be explained by the fact that the nanotube–nanotube interactions will be dominant at higher CNTs content, and lead to the formation of the interconnected or network‐like structures of SWCNTs in the polymer nanocomposites. The rheological loss factor indicates two relaxation peaks at frequencies of 0.11 and 12.8 Hz due to the interaction between SWCNTs and polymer chains and glass transition, respectively. Dynamic mechanical properties were measured for the prepared composites. The results indicate that the storage modulus changes steadily, and the tanδ peaks are less intense for high SWCNTs content. Tensile tests were measured and depicted by an increase in the elastic modulus with increasing SWCNTs content, but it decreases for all composites as the testing temperature increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology and thermal behavior of poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/poly(butylene adipate‐co‐terephthalate)/clay nanocomposites

Biopolymers are gaining increasing interest because of decline of mineral oil reserves, increasing waste problem, and increasing consciousness of society for environmental problems. However, competitiveness of biopolymers compared with conventional plastics is still limited due to partly insufficient properties and high prices. This study investigates the influence of blending of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) with poly(butylene adipate‐co‐terephthalate) (PBAT) as well as the influence of addition of functionalized montmorillonite (OMMT) to the blends on morphology and thermal behavior. Dispersion state and morphology of the nanocomposites are studied by X‐ray diffraction as well as scanning electron microscopy. Thermal stability is studied by thermogravimetric analysis and crystallization behavior is studied by differential scanning calorimetry and polarized optical microscopy. With respect to the morphology for the blends it can be seen that the immiscible biopolymers PHBV and PBAT are distributed in interlocking zones. There is a good dispersion and homogeneous distribution of OMMT within the biopolymer blends. The addition of 50% or more PBAT to PHBV as well as the insertion of OMMT enhances thermal stability of PHBV. In the blends, the addition of PBAT retards crystallization of PHBV. The OMMT acts as nucleating agent leading in total to more but less perfect crystals in the blends, and the crystallization slows further due to constraint in the movement of polymer chains. These results contribute to the understanding of the structure–properties relationship of bionanocomposite materials for packaging applications. POLYM. COMPOS., 36:2051–2058, 2015. © 2014 Society of Plastics Engineer     

Nanoclay‐reinforced poly(butylene adipate‐co‐terephthalate) biocomposites for packaging applications

Increasing generation and inadequate disposal of waste progressively compromise our environment. Solutions are proposed by the development of biodegradable polymers, that is, for short‐term applications like packaging. The present study focuses on the design and characterization of biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) nanocomposites reinforced by different types of nanoclays. The addition of natural and modified montmorillonite and bentonite to PBAT by melt mixing enhances slightly the thermal stability and increases the crystallization temperature, independently of the fillers' dispersion state. By contrast, storage modulus in dynamic mechanical analysis is increased when adding nanoclay, and improvement is higher for well‐dispersed organomodified fillers. Dispersion states and morphology of the nanocomposites are studied by X‐ray diffraction as well as scanning and transmission electron microscopy. PBAT‐based composites with modified bentonite reveal to show the best performance at room temperature (which is the temperature of interest for potential packaging applications) in comparison with the other investigated nanocomposites.POLYM. COMPOS., 33:2022–2028, 2012. © 2012 Society of Plastics Engineers     

Kinetics of water absorption and thermal properties of poly(lactic acid)/organomontmorillonite/poly(ethylene glycol) nanocomposites

Poly(lactic acid) (PLA)/organomontmorillonite (OMMT) nanocomposites were prepared by a melt intercalation technique. The effects of OMMT and poly(ethylene glycol) (PEG) on the thermal properties and water absorption behavior of PLA were investigated. The melting temperature and degree of crystallinity were comparable for the PLA and its nanocomposites. The glass transition temperature and crystallization temperature of PLA were decreased by the addition of PEG. X‐ray diffraction results revealed the formation of PLA nanocomposites, as the OMMT was partly intercalated and partly exfoliated. The maximum moisture absorption of PLA was increased in the presence of PEG and the diffusivity of the PLA nanocomposites decreased with increasing concentrations of PEG. However, the activation energy of the nanocomposites increased as the loading of PEG increased. These results indicated that the incorporation of OMMT and PEG enhanced the water‐barrier properties of the PLA. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Fabrication and characterization of electrospun fibrous nanocomposite scaffolds based on poly(lactide‐co‐glycolide)/poly(vinyl alcohol) blends

Tissue engineering involves the fabrication of three‐dimensional scaffolds to support cellular in‐growth and proliferation. Ideally, the scaffolds should be similar to the native extracellular matrix (ECM). Electrospun polymer nanofibrous scaffolds are appropriate candidates for ECM mimetic materials since they mimic the nanoscale properties of ECM. Electrospun polymer nanocomposites based on poly(lactide‐co‐glycolide) (PLGA)/poly(vinyl alcohol) (PVA) and organically modified montmorillonite (OMMT) were prepared by a solution intercalation technique followed by electrospinning. The morphology of fibrous scaffolds based on these nanocomposites was investigated using scanning electron microscopy. The scaffolds showed highly porous structure within the nanofibres of diameters ranging from 400 to 700 nm. X‐ray diffractometry gave evidence of good dispersion of the OMMT in the blends with exfoliated morphology. Measurements of the water uptake and water contact angle of the fibrous scaffolds indicated significant improvement in the hydrophilicity of the scaffolds. Evaluations of the mechanical properties and unrestricted somatic stem cell culture of the electrospun fibrous nanocomposite scaffolds revealed that the PLGA90/PVA10/1.5% OMMT and PLGA90/PVA10/3% OMMT samples are the most useful from the tissue engineering application viewpoint. Copyright © 2010 Society of Chemical Industry     

Prepared hydrogenated nitrile rubber (HNBR)/organo–montmorillonite nanocomposites by the melt intercalation method

The polymer, Hydrogenated Nitrile‐Butadiene Rubber (HNBR) was melt compounded with organophilic montmorillonite (OMMT). The dispersion of the OMMT in the HNBR matrix was characterized by X‐ray diffraction (XRD), which indicated that at the temperature of 100°C, the organoclay belong to the exfoliated and interlayer structure. The effect of sulfur on the dispersion of OMMT in the polymer matrix was also studied. The vulcanization changed the dispersion of OMMT in polymer matrix greatly and the basal spacing of clay layers is decreased after vulcanization. The mechanical properties, Akron abrasion and the crude oil medium aging‐resistant of HNBR nanocomposites were examined as a function of the OMMT content in the matrix of polymer. The results of the test show remarkable improvement in tensile strength, tear strength, aging‐resistant, and hardness of HNBR nanocomposites than that of unfilled HNBR. It is obvious that the 10 phr of OMMT filled nanocomposites have the best mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(ethylene 2,6-naphthalate)/layered silicate nanocomposites: fabrication, crystallization behavior and properties

In this study, poly(ethylene 2,6-naphthalate) (PEN)/layered silicate nanocomposites (PLSNs) were successfully prepared by the intercalation of PEN polymer into organically-modified layered montmorillonite through the melt blending process. Both X-ray diffraction data and transmission electron microscopy images of PEN/layered silicate nanocomposites indicate most of the swellable silicate layers were exfoliated and randomly dispersed into the PEN matrix. Mechanical and barrier properties of the fabricated nanocomposites performed by dynamic mechanical analysis and permeability analysis show significant improvements in the storage modulus and water permeability when compared to neat PEN. Differential scanning calorimeter (DSC) was used to investigate the isothermal crystallization behavior and melting behavior of PLSNs. DSC isothermal results revealed that the crystal growth process of PEN and PLSNs are a three-dimensional spherulitic growth. The activation energy of PEN increases with increasing content of layered silicates. The result indicates that the addition of layered silicate into PEN reduces the transportation ability of polymer chains during crystallization processes.     

Structure and properties of poly(lactic acid)/poly(ε‐caprolactone) nanocomposites with kinetically induced nanoclay location

Poly(lactic acid)/poly(ε‐caprolactone)/organically modified montmorillonite (PLA/PCL/OMMT) nanocomposites were melt‐processed in a twin‐screw extruder under high shear conditions. As a result of the processing conditions employed, the OMMT layers located in the less compatible PCL phase in all the ternary nanocomposites. The morphology of the PLA/PCL blend evolved from “sea‐island” to co‐continuous upon the addition of OMMT. Both the X‐ray diffraction (XRD) and viscoelastic characterization suggested similar OMMT dispersion in the reference PLA binary and in the PLA/PCL ternary nanocomposites, regardless of its location in the PLA and PCL phase, respectively. The reinforcing effect of the organoclay was also similar. The addition of OMMT to the PLA/PCL blend fully compensated the loss in stiffness and oxygen barrier performance produced by PCL in PLA; the nanocomposite with 3% OMMT showed the same modulus and permeability values as those of pure PLA. Moreover, the ductile behavior (elongation at break > 80%) of the PLA/PCL blend remained constant even in the nanocomposite containing 5% OMMT. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43815.