三元乙丙橡胶/蒙脱土纳米复合材料制备中硫化体系的比较

采用了熔融插层和两种硫化体系硫磺 促进剂和过氧化物体系制备了三元乙丙橡胶 蒙脱土纳米复合材料 ,并将这两种体系形成的纳米复合材料进行了形态、力学性能和光学性能的比较 ,同时采用Flory Rehner方程对它们的硫化行为进行了评价 .X射线衍射 (XRD)、透射电镜 (TEM)、力学性能和光学性能的测试结果表明 ,由硫磺硫化体系制备的纳米复合材料为不透明和剥离型 .其原有的d0 0 1 衍射峰消失 ,有序层被剥离成 10 0～ 2 0 0nm的片层均匀分散在EPDM基体中 ,其力学性能有了极大的提高 ;而过氧化物体系制备的纳米复合材料为半透明和插层型 .对两种体系的硫化行为的评价结果表明 ,随着有机蒙脱土加入量的增加 ,硫磺 促进剂硫化体系的t90 延长 ,交联密度减小 ,最大 最小转矩也变小 ;而过氧化物硫化体系的相应值却变化不大     

Preparation,characterization and thermal behavior of poly(vinyl alcohol)/organic montmorillonite nanocomposites through solid-state shear pan-milling

In this study, the solid-state shear pan-milling was employed to prepare a series of polymer/layered silicate (PLS) nanocomposites. During the process of pan-milling at ambient temperature, poly(vinyl alcohol)/organic montmorillonite (PVA/OMMT) can be effectively pulverized, resulting in coexistence of intercalated and exfoliated OMMT layers. The obtained PLS nanocomposites were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). TEM analysis indicated that OMMT dispersed homogeneously in PVA matrix and XRD results illustrated that pan-milling had an obvious effect on increase in the interlayer spacing of OMMT, and resulted in coexistence of intercalated and exfoliated OMMT layers formed. Thermal gravimetric analysis showed that thermal stability of PVA was improved owing to the incorporation of OMMT. Thermal decomposition kinetics of PVA/OMMT nanocomposites with different milling cycles of OMMT was also studied. Two types of OMMT are chosen to compare the effect of hydrophilicity of OMMT on PVA/OMMT nanocomposites.     

Structure and mechanical properties of poly(l-lactide)/layered silicate nanocomposites

Poly(ε-caprolactone) (PCL) masterbatches with the intercalated and the exfoliated morphology were prepared by ring opening polymerization of ε-caprolactone in the presence of organomodified montmorillonite (MMT) Cloisite 30B. Poly(l-lactide) (PLLA) nanocomposites with Cloisite 30B or PCL masterbatches were prepared by melt blending. The effects of the silicate type, MMT content and the nanocomposite morphology on thermal and mechanical properties of PLLA nanocomposites were examined. The montmorillonite particles in PLLA/Cloisite 30B and PLLA/intercalated masterbatch nanocomposites were intercalated. In contrary to expectations, the exfoliated silicate layers of exfoliated masterbatch were not transferred into the PLLA matrix. Due to a low miscibility of PCL and PLLA, MMT remained in the phase-separated masterbatch domains. The stress-strain characteristics of PLLA nanocomposites, Young modulus E, yield stress σ_y and yield strain ε_y, decreased with increasing MMT concentration, which is associated with the increase in PCL content. The expected stiffening effect of MMT was low due to a low aspect ratio of its particles and was obscured by both plastifying effects of PCL and low PLLA crystallinity. Interestingly, in contrast to the neat PLLA, ductility was enhanced in all PLLA/Cloisite 30B materials and in PLLA/masterbatch nanocomposites with low MMT concentrations.     

Toughening of ethylene-propylene random copolymer/clay nanocomposites: Comparison of different compatibilizers

Ethylene/propylene-random-copolymer(PPR)/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers,including an ethylene-octene copolymer grafted maleic anhydride(POE-g-MA) and three maleic-anhydride-grafted polypropylenes(PP-g-MA) with different melt flow indexes(MFI),were used to improve the dispersion of organic clay in matrix.On the other hand,the effects of organic montmorillonite(OMMT) content on the nanocomposite structure in terms of clay dispersion in PPR matrix,thermal behavior and tensile properties were also studied. The X-ray diffraction(XRD) and transmission electron microscopy(TEM) results show that the organic clay layers are mainly intercalated and partially exfoliated in the nanocomposites.Moreover,a PP-g-MA compatibilizer(compatibilizer B) having high MFI can greatly increase the interlayer spacing of the clay as compared with other compatibilizers.With the introduction of compatibilizer D(POE-g-MA),most of the clays are dispersed into the POE phase,and the shape of the dispersed OMMT appears elliptic,which differs from the strip of PP-g-MA.Compared with virgin PPR,the Young’s modulus of the nanocomposite evidently increases when a compatibilizer C(PP-g-MA) with medium MFI is used.For the nanocomposites with compatibilizer B and C,their crystallinities(X_c) increase as compared with that of the virgin PPR. Furthermore,the increase of OMMT loadings presents little effect on the melt temperature(T_m) of the PPR/OMMT nanocomposites,and slight effect on their crystallization temperature(T_c).Only compatibilizer B can lead to a marked increases in crystallinity and T_c of the nanocomposite when the OMMT content is 2 wt%.     

Shear‐induced change of exfoliation and orientation in polypropylene/montmorillonite nanocomposites

For the improved dispersion of montmorillonite (MMT) in a polypropylene (PP) matrix, PP/MMT nanocomposites prepared via direct melt intercalation were further subjected to oscillating stress achieved by dynamic packing injection molding. The shear‐induced morphological changes were investigated with an Instron machine, wide‐angle X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The original nanocomposites possessed a partly intercalated and partly exfoliated morphology. A transformation of the intercalated structure into an exfoliated structure occurred after shearing, and a more homogeneous dispersion of MMT in the PP matrix was obtained. However, the increase of the exfoliated structure was accompanied by the scarifying of the orientation of MMT layers along the shear direction. Some bended or curved MMT layers were found for the first time by TEM after shearing. However, the orientation of PP chains in the PP/MMT nanocomposites became very difficult under an external shear force; this indicated that the molecular motion of PP chains intercalated between MMT layers was highly confined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1–10, 2003     

Preparation of thermosetting polyurethane nanocomposites by montmorillonite modified with a novel intercalation agent

A novel thermosetting polyurethane (TSPU)/organic montmorillonite (OMMT) nanocomposite has been synthesized. N‐diamino octadecyl trimethyl ammonium chloride (DODTMAC) was used as an intercalation agent to treat Na⁺‐montmorillonite (MMT) and form a novel kind of OMMT. Fourier transform infrared spectroscopy (FT‐IR), wide angle X‐ray diffraction (WAXD), and thermogravimetric analysis (TGA) data indicated that the MMT was successfully intercalated by this intercalation agent, as evidenced by the fact that the basal spacing of MMT galleries was expanded from 1.5 to 3.2 nm. This OMMT was used to prepare the TSPU nanocomposites. Both the reinforcing and compatibilizing performance of the filler were investigated. Tensile tests showed that the tensile strength of TSPU/OMMT‐4 was the highest, and was about 3.62 times higher than that of the pure TSPU, and also the elongation at break showed an enhancement. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) measurements illustrated that the glass transition temperature of the TSPU/OMMT‐4 nanocomposite was improved from 0.5 to 6.5 °C, which corresponded to the restriction of the soft segments of TSPU. The highest initial and center temperatures of TSPU/OMMT‐4 obtained from TGA were due to the highest retard effect of the TSPU molecular chains. WAXD studies showed that the formation of the nanocomposites in all the cases with the almost disappearance of the peaks corresponding to the basal spacing of MMT. SEM and TEM were used to investigate the morphologies of the TSPU/OMMT‐4 nanocomposite, and demonstrated that the nanocomposite was comprised of a well dispersion of a mixture of intercalated and exfoliated silicate layers throughout the matrix. It was proposed that the nano‐reinforcing effect caused by the well‐dispersed silicate layers might reduce the amount and size of voids and increase the length of the crack‐spreading path during tensile drawing. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 519–531, 2007.     

Characterization of polypropylene/layered silicate nanocomposites prepared by single-step method

The extent of organo-modified clay (C93A) platelets dispersion in polymer matrix and crystallization and melting behavior of iPP-based nanocomposites prepared by a single-step melt-mixing method were investigated by wide-angle X-ray diffraction (WAXD), transmission (TEM), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). WAXD patterns revealed exfoliated structure of nanocomposites containing 1 wt% clay, and mixed intercalated/exfoliated structure at higher concentration of nanoclay. The isothermal crystallization proceeds faster in the matrix polymer (iPP/PP-g-MA) than in nanocomposite samples. The results obtained for T _m ^o suggest that the presence of nanoclay has induced a perfection of the formed crystals. The presence of C93A particles in PP leads to increase in crystallization peak temperature implying nucleating ability of clay particles, which was more pronounced in exfoliated than in mixed intercalated/exfoliated system.     

Preparation and characterization of poly(propylene carbonate)/montmorillonite nanocomposites by solution intercalation

Poly(propylene carbonate) (PPC) is a new biodegradable aliphatic polycarbonate. However, the poor thermal stability and low glass transition temperatures (T_g) have limited its applications. To improve the thermal properties of PPC, organophilic montmorillonite (OMMT) was mixed with PPC by a solution intercalation method to produce nanocomposites. An intercalated-and-flocculated structure of PPC/OMMT nanocomposites was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The thermal and mechanical properties of PPC/OMMT nanocomposites were investigated by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), and electronic tensile tester. Due to the nanometer-sized dispersion of layered silicate in polymer matrix, PPC/OMMT nanocomposites exhibit improved thermal and mechanical properties than pure PPC. When the OMMT content is 4 wt%, the PPC/OMMT nanocomposite shows the best thermal and mechanical properties. These results indicate that nanocomposition is an efficient and convenient method to improve the properties of PPC.     

Influence of degree of intercalation on the crystal growth kinetics of poly[(butylene succinate)-co-adipate] nanocomposites

The influence of the degree of intercalation of polymer chains in the two dimensional silicate galleries on the crystallization behavior of poly[(butylene succinate)-co-adipate] (PBSA) is being reported on. The nanocomposites were prepared by melt-blending of PBSA and organically modified montmorillonite (OMMT) in a batch-mixer. Two different types of commercially available OMMTs, with different extents of miscibility of organic modifiers with PBSA, were used, leading to highly delaminated and stacked/intercalated nanocomposite structures as revealed by X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM) observations. The non-isothermal crystallization behavior of PBSA and the nanocomposite samples were studied by differential scanning calorimetry (DSC). Crystal growth kinetics studies showed that when silicate layers are highly delaminated into the PBSA matrix, nucleation behaviors decreased significantly, relative to the stacked/intercalated silicate layers. These observations indicate that the overall crystal growth kinetics retard in delaminated nanocomposites, opposed to increasing in the case of stacked/intercalated nanocomposites. Polarized optical microscopy (POM) observations and light scattering studies indicate that PBSA spherulites are fairly large and more perfectly grown in the case of delaminated nanocomposites, relative to the pure PBSA matrix. The effect of high levels of dispersion of silicate layers in the PBSA matrix on cold crystallization behavior was also studied.     

Studies of ABS-graft-maleic anhydride/clay nanocomposites: Morphologies, thermal stability and flammability properties

ABS-g-MAH (maleic anhydride) with different grafting degree, ABS/OMT (organo montmorillonite) and ABS-g-MAH/OMT nanocomposites were prepared via melt blending. The grafting reaction, phase morphology, clay dispersion, thermal properties, dynamic mechanical properties and flammability properties were investigated. FTIR spectra results indicate that maleic anhydride was successfully grafted onto butadiene chains of the ABS backbone in the molten state using dicumyl peroxide as the initiator and styrene as the comonomer and the relative grafting degree increased with increasing loading of MAH. TEM images show the size of the dispersed rubber domains of ABS-g-MAH increased and the dispersion is more uniform than that of neat ABS resin. XRD and TEM results show that intercalated/exfoliated structure formed in ABS-g-MAH/OMT nanocomposites and the rubber phase intercalated into clay layers distributed in both SAN phase and rubber phase. TGA results reveal the intercalated/exfoliated structure of ABS-g-MAH/OMT nanocomposites has better barrier properties and thermal stability than intercalated ones of ABS/OMT nanocomposites. The T_g of ABS-g-MAH/OMT nanocomposites was also higher than that of neat ABS/OMT nanocomposites. The results of cone measurements show that ABS-g-MAH/OMT nanocomposites exhibit significantly reduced flammability when compared to ABS/OMT nanocomposites even at the same clay content. The chars of ABS-g-MAH/OMT nanocomposites were tighter, denser, more integrated and fewer surface microcracks than ABS/OMT residues.     

Preparation and characterization of PP/clay nanocomposites based on modified polypropylene and clay

X‐ray diffraction and differential scanning calorimeter (DSC) methods have been used to investigate the crystallization behavior and crystalline structure of hexamethylenediamine (HMDA)‐modified maleic‐anhydride‐grafted polypropylene/clay (PP‐g‐MA/clay) nanocomposites. These nanocomposites have been prepared by using HMDA to graft the PP‐g‐MA (designated as PP‐g‐HMA) and then mixing the PP‐g‐HMA polymer in hot xylene solution, with the organically modified montmorillonite. Both X‐ray diffraction data and transmission electron microscopy images of PP‐g‐HMA/clay nanocomposites indicate that most of the swellable silicate layers are exfoliated and randomly dispersed into PP‐g‐HMA matrix. DSC isothermal results revealed that introducing 5 wt % of clay into the PP‐g‐HMA structure causes strongly heterogeneous nucleation, which induced a change of the crystal growth process from a three‐dimensional crystal growth to a two‐dimensional spherulitic growth. Mechanical properties of PP‐g‐HMA/clay nanocomposites performed by dynamic mechanical analysis show significant improvements in the storage modulus when compared to neat PP‐g‐HMA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3242–3254, 2005     

Effect of extrusion and photo-oxidation on polyethylene/clay nanocomposites

Polyethylene (a 1:1 blend of m-LLDPE and z-LLDPE) double layer silicate clay nanocomposites were prepared by melt extrusion using a twin screw extruder. Maleic anhydride grafted polyethylene (PEgMA) was used as a compatibiliser to enhance the dispersion of two organically modified monmorilonite clays (OMMT): Closite 15A (CL15) and nanofill SE 3000 (NF), and natural montmorillonite (NaMMT). The clay dispersion and morphology obtained in the extruded nanocomposite samples were fully characterised both after processing and during photo-oxidation by a number of complementary analytical techniques. The effects of the compatibiliser, the organoclay modifier (quartenary alkyl ammonium surfactant) and the clays on the behaviour of the nanocomposites during processing and under accelerated weathering conditions were investigated. X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy (SEM), rheometry and attenuated reflectance spectroscopy (ATR-FTIR) showed that the nanocomposite structure obtained is dependent on the type of clay used, the presence or absence of a compatibiliser and the environment the samples are exposed to. The results revealed that during processing PE/clay nanocomposites are formed in the presence of the compatibiliser PEgMA giving a hybrid exfoliated and intercalated structures, while microcomposites were obtained in the absence of PEgMA; the unmodified NaMMT-containing samples showed encapsulated clay structures with limited extent of dispersion in the polymer matrix. The effect of processing on the thermal stability of the OMMT-containing polymer samples was determined by measuring the additional amount of vinyl-type unsaturation formed due to a Hoffman elimination reaction that takes place in the alkyl ammonium surfactant of the modified clay at elevated temperatures. The results indicate that OMMT is responsible for the higher levels of unsaturation found in OMMT-PE samples when compared to both the polymer control and the NaMMT-PE samples and confirms the instability of the alkyl ammonium surfactant during melt processing and its deleterious effects on the durability aspects of nanocomposite products. The photostability of the PE/clay nanocomposites under accelerated weathering conditions was monitored by following changes in their infrared signatures and mechanical properties. The rate of photo-oxidation of the compatibilised PE/PEgMA/OMMT nanocomposites was much higher than that of the PE/OMMT (in absence of PEgMA) counterparts, the polymer controls and the PE–NaMMT sample. Several factors have been observed that can explain the difference in the photo-oxidative stability of the PE/clay nanocomposites including the adverse role played by the thermal decomposition products of the alkyl ammonium surfactant, the photo-instability of PEgMA, unfavourable interactions between PEgMA and products formed in the polymer as a consequence of the degradation of the surfactant on the clay, as well as a contribution from a much higher extent of exfoliated structures, determined by TEM, formed with increasing UV-exposure times.     

Effects of organo-montmorillonite dispersion on thermal stability of epoxy resin nanocomposites

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo-montmorillonite (O-MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The dispersion state of the MMT in the matrix was investigated by X-ray diffraction and scanning electronic microscopy. The thermal stability of the epoxy nanocomposites was examined by TGA. Thermal stability of the epoxy nanocomposite is dependent upon the dispersion state of the OMMT in the epoxy matrix although all the epoxy nanocomposites had enhanced thermal stability compared with the neat epoxy resin. The thermal stability of the epoxy resin nanocomposites was correlated with the dispersion state of the MMT in the epoxy resin matrix.     

Nanocomposites with Biodegradable Polycaprolactone Matrix

Summary: Biodegradable polymer/clay nanocomposites and/or composites based on poly(ε-polycaprolactone) (PCL) were prepared by conventional melt mixing. Three kinds of clays, organomodified Cloisite 15A and Cloisite 10A with different ammonium cations located in the silicate gallery and unmodified Cloisite with Na cations were used for composites preparation. The degree of dispersion of silicate layers in the matrix was determined by X-ray diffraction and transmission electron microscopy. Oscillatory rheological measurements were used for characterization of the physical network formed by the filler. The presence of intercalated and exfoliated structures were observed for the composites PCL/Cloisite 15A and PCL/Cloisite 10A, indicating that nanocomposite structure was formed. Changes of viscoelastic properties to more solid-like behavior, especially in the low frequency range were explained by formation of silicate network structure, which can be detected by modified Cole-Cole plots.     

Nanoalloy Based on Clays: Intercalated‐Exfoliated Layered Silicate in High Performance Elastomer

A novel method is described for the preparation of nanocomposites comprising a high performance rubber for tire application and layered silicates clay. In this work nanocomposites of solution‐styrene butadiene rubber (S‐SBR) with montmorillonite layered silicate were prepared with carboxylated nitrile rubber (XNBR), a polar rubber, as a compatibilizer. A sufficient amount of organomodified layered silicate was loaded in carboxylated nitrile rubber (XNBR) and this compound was blended as a master batch in the S‐SBR. Mixed intercalated/exfoliated morphologies in the nanocomposite are evinced by X‐ray diffraction measurements and transmission electron microscopy. Dynamic mechanical analysis also supports the compatibility of the composites. A good dispersion of the layered silicate in the S‐SBR matrix was reflected from the physical properties of the nanocomposites, especially in terms of tensile strength and high elongation properties.     

Phase behavior of modified montmorillonite– poly(ϵ‐caprolactone) nanocomposites

The thermal behavior and overall isothermal crystallization kinetics of a series of organophilic modified montmorillonite–poly(?‐caprolactone) nanocomposites were investigated. In general, the thermal behavior was influenced more by the type of dispersion than by the clay content. For nanocomposites in which silicate platelets were predominantly dispersed in the polymer matrix to give exfoliated structures, the thermal properties were improved with respect to those of neat poly(?‐caprolactone), whereas in those cases in which simply intercalated structures were attained, the thermal properties regularly decayed as the clay content increased. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1321–1332, 2004     

Characterization and thermal degradation of polypropylene-montmorillonite nanocomposites

Polypropylene (PP)-montmorillonite nanocomposites have been prepared using isotactic PP homopolymers with different rheological properties, and a maleic anhydride grafted PP. Morphology and structure of the composites were investigated by using X-ray techniques (WAXD, SAXS) and transmission electron microscopy (TEM). The absence of pristine clusters of the clay and the presence of intercalated and exfoliated structures were shown for all the investigated samples. The nanocomposite prepared by using maleic anhydride grafted PP showed a widespread exfoliation. The thermal behaviour and degradation have been studied by means of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The incorporation of the montmorillonite improves the thermal stability in air atmosphere of all the investigated PPs, thanks to a physical barrier effect of the silicate layers.     

The fabrication of affinity improved nanocomposites with plasma treated polypropylene (PP) and alkaline cellulose nanofiber (CNF) suspension

Polypropylene (PP) nanocomposites containing cellulose nanomaterials have been studied for the last decade, but are still challenging due to the lack of affinity between PP and cellulose nanofiber (CNF), and the uneven dispersion of CNF in the PP matrix. In order to achieve the uniform dispersion of CNF in the PP matrix and improve affinity between PP and CNF, plasma-treated PP/aCNF nanocomposites were prepared by adding an alkaline CNF (aCNF) suspension to the nitrogen (N₂) and oxygen (O₂) plasma-treated PP. Based on the results of various analyses, the N₂ plasma-treated PP (npPP)/aCNF nanocomposite showed the best performance in tensile and oxygen barrier properties. The npPP/aCNF nanocomposite increased 32.8 and 26.3% in yield stress and Young's modulus, respectively, compared with neat PP, also in O₂ permeability, it showed a value of 94.31 cc-mm/m²-day-atm and showed a statistically significant decrease in contrast to neat PP. The npPP/aCNF nanocomposite has a great feasibility to be applied in various barrier packaging applications.     

Thermal and mechanical properties of syndiotactic polystyrene/organoclay nanocomposites with different microstructures

The fabrication of syndiotactic polystyrene (sPS)/organoclay nanocomposite was conducted via a stepwise mixing process with poly(styrene‐co‐vinyloxazolin) (OPS), that is, melt intercalation of OPS into organoclay followed by blending with sPS. The microstructure of nanocomposite mainly depended on the arrangement type of the organic modifier in clay gallery. When organoclays that have a lateral bilayer arrangement were used, an exfoliated structure was obtained, whereas an intercalated structure was obtained when organoclay with a paraffinic monolayer arrangement were used. The thermal and mechanical properties of sPS nanocomposites were investigated in relation to their microstructures. From the thermograms of nonisothermal crystallization and melting, nanocomposites exhibited an enhanced overall crystallization rate but had less reduced crystallinity than a matrix polymer. Clay layers dispersed in a matrix polymer may serve as a nucleating agent and hinder the crystal growth of polymer chains. As a comparison of the two nanocomposites with different microstructures, because of the high degree of dispersion of its clay layer the exfoliated nanocomposite exhibited a faster crystallization rate and a lower degree of crystallinity than the intercalated one. Nanocomposites exhibited higher mechanical properties, such as strength and stiffness, than the matrix polymer as observed in the dynamic mechanical analysis and tensile tests. Exfoliated nanocomposites showed more enhanced mechanical properties than intercalated ones because of the uniformly dispersed clay layers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1685–1693, 2004