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1.
Water-assisted extrusion process has been used to successfully prepare polypropylene (PP)/clay nanocomposites with high degree of clay delamination and markedly improved rheological, thermal and mechanical properties. PP-graft-maleic anhydride (PP-g-MA)-based nanocomposites and masterbatches were synthesized from untreated clay and organoclay, respectively, and fully characterized. The effects of using high-shear rates and water injection during the melt-compounding were examined. A mechanism explaining the formation of such nanocomposites is then proposed. The best clay dispersion and properties improvements of PP-g-MA/organoclay nanocomposites and masterbatches were obtained using high-shear rates and water injection (synergy effect). PP-based nanocomposites were then synthesized by dilution of PP-g-MA-based masterbatches into neat PP. For comparison, nanocomposites were also prepared by a one-pot process where PP, PP-g-MA and organoclay are directly melt-blended with or without water injection. The nanocomposites prepared by dilution into PP of a masterbatch prepared through water-assisted extrusion showed the highest clay dispersion and consequently the best thermal, mechanical and rheological properties.  相似文献   

2.
In this study, we investigated the performances of a hydroxy ethyl methacrylate grafted PP (PP-g-HEMA) and a glycidyl methacrylate grafted PP (PP-g-GMA) as compatibilizers in PP/clay nanocomposites. The compatibilizers were prepared by melt grafting with a radical initiator. Since the PP-g-MA is successfully and widely used in the PP/clay nanocomposites, we also studied three PP-g-MAs containing different amounts of MA and having different molecular weights for a comparison. PP/clay nanocomposites compatibilized by the PP-g-HEMA and the PP-g-GMA show a similar level of the clay interlayer distances with those of the PP-g-MAs. We also investigated the effect of molecular weights of the compatibilizers. In general, the compatibilizer of lower molecular weight was observed to exhibit lower performance as a compatibilizer. It is observed that an increase of polar group content in the modified PP (PP-g-HEMA, PP-g-GMA, and PP-g-MA) always accompanies the molecular weight reduction, which deteriorates the mechanical properties. Thus, we prepared the PP-g-HEMA and PP-g-GMA by incorporation of a styrene comonomer. The compatibilizers (PP-g-HEMA-co-styrene and PP-g-GMA-co-styrene) thus obtained show good performance as a compatibilizer in the PP/clay nanocomposites. We observed that the PP/clay composites containing the PP-g-HEMA-co-styrene and the PP-g-GMA-co-styrene have very well-balanced mechanical properties.  相似文献   

3.
Lili Cui 《Polymer》2007,48(6):1632-1640
The compatibilization effects provided by amine functionalized polypropylenes versus those of a maleated polypropylene, PP-g-MA, for forming polypropylene-based nanocomposites were compared. Amine functionalized polypropylenes were prepared by reaction of maleated polypropylene, PP-g-MA, with 1,12-diaminododecane in the melt to form PP-g-NH2 which was subsequently protonated to form PP-g-NH3+. Nanocomposites were prepared by melt processing using a DSM microcompounder (residence time of 10 min) by blending polypropylene and these functionalized materials with sodium montmorillonite, Na-MMT, and with an organoclay. X-ray and transmission electron microscopy plus tensile modulus tests were used to characterize those nanocomposites. Composites based on Na-MMT as the filler showed almost no improvement of tensile modulus compared to the polymer matrix using any of these functionalized polypropylenes, which indicated that almost no exfoliation was achieved. All the compatibilized nanocomposites using an organoclay, based on quaternary ammonium surfactant modified MMT, as the filler had better clay exfoliation compared to the uncompatibilized PP nanocomposites. Binary and ternary nanocomposites using amine functionalized polypropylenes had good clay exfoliation, but no advantage over those using PP-g-MA. The PP-g-MA/organoclay and PP/PP-g-MA/organoclay nanocomposites showed the most substantial improvements in terms of both mechanical properties and clay exfoliation.  相似文献   

4.
This work discloses a novel one‐pot preparation method of polypropylene (PP)/clay nanocomposites with high degree of clay delamination and improved thermal, mechanical and rheological properties. The in situ simultaneous synthesis of carboxylate clay from native clay and ionomer of PP‐graft maleic anhydride (PP‐g‐MA) through trihydrate sodium acetate addition, combined with water injection in the extrusion process, appears to be a valuable alternative to the use of organoclay for producing PP/PP‐g‐MA/clay nanocomposites. The influence of PP‐g‐MA graft content, and of its ionomer form, onto the clay dispersion has been especially investigated. PP‐g‐MA of low graft content is compared to a home‐made highly grafted PP‐g‐MA synthesized in the presence of N‐bromosuccinimide (NBS). The nanocomposites prepared by combining the use of NBS‐mediated PP‐g‐MA, trihydrate sodium acetate and water injection exhibit the highest clay dispersion. Thermal, rheological, and mechanical properties of the nanocomposites have been measured. POLYM. COMPOS., 36:644–650, 2015. © 2014 Society of Plastics Engineers  相似文献   

5.
B. Lecouvet  J. Devaux 《Polymer》2011,52(19):4284-4295
Naturally occurring halloysite nanotubes (HNTs) are used to prepare Polypropylene (PP)/HNTs nanocomposites using a novel “one step” water-assisted extrusion process with and without the use of a PP-graft-maleic anhydride (PP-g-MA) as compatibilizer. In order to analyze the influence of PP-g-MA and/or water injection on the HNTs dispersion and therefore on nanocomposite properties, structural analysis (SEM and TEM) is combined with rheological and thermo-mechanical experiments. The best clay dispersion is obtained when compatibilizer and water injection are combined together (synergistic effect). As a consequence, the linear viscoelastic properties and the dynamic storage modulus are dramatically enhanced for this system. A mechanism explaining the interaction between HNTs and PP-g-MA in presence of water is proposed. The thermal stability and flame retardant property are also investigated. Thermal analyses reveal two opposite effects of HNTs on the thermal behaviour of PP. A surface catalytic action of the halloysite speeds up thermal degradation of PP. However, this effect is reduced with improved HNTs dispersion, presumably via an entrapment mechanism of the decomposition products inside the lumens. Finally, cone calorimeter results show that low flammability of nanocomposites is only achieved when combining water injection and PP-g-MA. In view of these results, PP/HNTs nanocomposites prepared using this novel processing route are promising candidates for flame retardant applications.  相似文献   

6.
Rajkiran R. Tiwari 《Polymer》2011,52(4):1141-1154
The effect of organically modified clay on the morphology, phase stability and mechanical properties of polypropylene (PP) and polystyrene (PS) blends was studied using three molecular weight grades of PP. Maleated polypropylene was used, at a PP-g-MA/organoclay ratio of 1, to preferentially promote dispersion of the organoclay in the PP matrix. The MMT content was fixed at 3 wt% based on the PP/PP-g-MA/MMT phase and the PS content was varied from 0-100 wt% in the blend. All blends were processed using a twin screw extruder. The organoclay resides in the PP phase and at the PP/PS interface. The dispersed PS particle size is significantly reduced by the presence of MMT, with maximum decrease observed for the low viscosity PP compared to its blend without MMT. The blends with MMT did not show any change in onset of co-continuity, though MMT shifts the phase inversion composition toward lower PS contents. The phase stability of the blend was significantly improved by the presence of MMT; for blends annealed at 210 °C for 2 h the dispersed phase particle size increased by as much as 10x without MMT with little change was noted with MMT present in the blend. The tensile modulus of blends improved with the addition of MMT at low PS contents. Blends based on the highest molecular weight grade PP showed increase in the tensile yield stress up to 40 wt% PS in the absence of MMT. The tensile strength at break for blend increased slightly with MMT while elongation at break and impact strength decreased in the presence of MMT. Surface energy analysis model was used to predict the orientation and equilibrium position of the clay platelet at the interface based on the surface energies.  相似文献   

7.
Polypropylene/clay nanocomposite (PCN) containing 1 wt% organo-modified clay was prepared by latex technology, previously successfully applied for preparation of carbon nanotubes (CNTs)/polymer composites. The level of dispersion of organoclay and the microstructure of the resulting PCNs were characterized by means of X-ray diffraction analysis, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The obtained results have demonstrated that the latex technique represents a promising method for preparation of PP/clay nanocomposites with good dispersion of exfoliated nanoclay particles. The influence of clay nanoparticles on nonisothermal crystallization of PCN was investigated by DSC. The crystallization onset temperature of the matrix rises for about 5 °C when crystallizing from the quiescent melt. Improved thermal stability of PP/nanoclay was observed as evaluated by TGA. The dynamic mechanical analysis reveals an increase in storage modulus of PP matrix in the nanocomposites for 30% over a temperature range, indicating an increase in the stiffness of the material with the addition of organically modified clay.  相似文献   

8.
Direct melt compounding was used to prepare nanocomposites of organophilic montmorillonite (o‐mmt) clay dispersed in maleated polypropylenes (PPgMA) as well as nanocomposites of organoclay and polypropylene (PP) modified with various grades of PPgMA compatibilizers. The thermal effect on the rheology and melt compounding was first investigated with a plasticorder. The shear viscosities and the melt flow indices (MFI) of the PPgMA compatibilizers were sensitive to the blending temperature, which had to be varied with the compatibilizer grade to achieve desirable level of torque for extensive exfoliation of organoclay in the plasticorder. However, for low molecular weight oligomer, the clay dispersion was poor because of low shear viscosity and thermal instability. Next, the PPgMA‐modified PP/organoclay nanocomposites were prepared on a corotating twin‐screw extruder. The nanoscale dimensions of the dispersed clay platelets led to significantly increased linear viscoelastic properties, which were qualitatively correlated with the state of exfoliation in the nanocomposites. The relative viscosity (relative to the silicate‐free matrix) curves revealed a systematic trend with the extent of clay exfoliation. Furthermore, the degree of clay dispersion was found to increase with the loading of compatibilizers; however, high loading of compatibilizer compromised the final moduli of the nanocomposites. POLYM. ENG. SCI. 46:289–302, 2006. © 2006 Society of Plastics Engineers  相似文献   

9.
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  相似文献   

10.
Polyamide 6/polypropylene (PA6/PP=70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic modified montmorillonite (organoclay) were prepared using twin screw extruder followed by injection molding. Maleated polypropylene (MAH-g-PP) was used to compatibilize the blend system. The mechanical properties of PA6/PP nanocomposites were studied through tensile and flexural tests. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the fracture surface morphology and the dispersion of the organoclay, respectively. X-ray diffraction (XRD) was used to characterize the formation of nanocomposites. The thermal properties were characterized by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The dynamic mechanical properties of PA6/PP nanocomposites were analyzed by using dynamic mechanical thermal analyzer (DMTA). The strength and stiffness of PA6/PP nanocomposites were improved significantly in the presence of MAH-g-PP. This has been attributed to the synergistic effect of organoclay and MAH-g-PP. The MAH-g-PP compatibilized PA6/PP nanocomposites showed a homogeneous morphology supporting the compatibility improvement between PA6, PP and organoclay. TEM and XRD results revealed the formation of nanocomposites as the organoclay was intercalated and exfoliated. A possible chemical interaction between PA6, PP, organophilic modified montmorillonite and MAH-g-PP was proposed based on the experimental work.  相似文献   

11.
Maleic anhydride grafted polypropylene (PP‐g‐MA) and organically modified clay composites were prepared in a plasticorder. PP‐g‐MAs, including Polybond PB3150, Polybond PB3200, Polybond PB3000, and Epolene E43, with a wide range of maleic anhydride (MA) concentrations and molecular weights were used. The structure was investigated with X‐ray diffraction (XRD) and transmission electron microscopy (TEM). PP‐g‐MA compatibilizers gave rise to similar degrees of dispersion beyond the weight ratio of 3/1, with the exception of E43, which had the highest MA content and the lowest molecular weight. The thermal instability and high melt index were responsible for the ineffective modification by E43. Furthermore, PP‐g‐MA with a lower molecular weight and a higher melt index had to be compounded at a lower mixing temperature to achieve a reasonable level of torque for clay dispersion. Polypropylene/organoclay nanocomposites were then modified with different levels of PP‐g‐MA compatibilizers with a twin‐screw extruder. The polypropylene/E43/clay system, as shown by XRD patterns and TEM observations, yielded the poorest clay dispersion of the compatibilizers under investigation. The curves of the relative complex viscosity also revealed a systematic trend with the extent of exfoliation and showed promise for quantifying the hybrid structure of the nanocomposites. The mechanical properties and thermal stability were determined by dynamical mechanical analysis and thermogravimetric analysis, respectively. Although PP‐g‐MA with a lower molecular weight led to better clay dispersion in the polypropylene nanocomposites, it caused deterioration in both the mechanical and thermal properties of the hybrid systems. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1667–1680, 2005  相似文献   

12.
Summary Polypropylene-clay nanocomposites were prepared by melt intercalation in a twin screw extruder using two mixing methods: two-step mixing and one-step mixing. The effect of using two different kinds of PP-g-MA (polypropylene-grafted maleic anhydride), with graft efficiencies of 0.1 and 1.0 wt% of MA and with different molecular weight, on clay dispersion and mechanical properties of nanocomposites was investigated. Three different clays, natural montmorillonite (Cloisite Na+) and chemically modified clays Cloisite 20A and Cloisite 30B were used. The relative influence of each factor was observed from structural analysis by WAXD, TEM, and mechanical properties. X-ray diffractometry (XRD) was used to investigate the intercalation effect in the nanocomposites. The results indicted that the intercalation effect and mechanical properties, specially modulus, tensile strength and impact strength, were enhanced by increasing the content of MA, using maleated PP with higher graft efficiency, and using the two step mixing conditions. Better dispersion and exfoliation were obtained when using clay 20A than 30B and natural Na+ montmorillonite. The results showed that clay dispersion and interfacial adhesion are greatly affected by the kind of maleated PP. The increase in content of polar groups gives as a result better interfacial adhesion and subsequent mechanical performance.  相似文献   

13.
The use of polypropylene (PP)‐layered silicate nanocomposite has attracted great interest in the polymer industry over the last years. On one hand, PP is widely used in many fields of applications because of good performance and cost. On the other hand, the major advantage of layered silicate nanofiller in the polymer matrix is the small amount of filler (<5 wt%) needed to enhance various properties such as Young's modulus. The most commonly used layered silicates are organomodified montmorillonite (MMT). In this study, a PP/organoclay nanocomposite, filled with layered silicate Nanofil SE3010 (1 and 5 wt%), provided by Rockwood Additives, USA, was used. The polymer nanocomposites were prepared via melt intercalation in a laboratory kneader. The compatibilizer (PP grafted with maleic acid anhydride) admixture content relative to the organoclay content (1 and 5 wt%) was chosen at a ratio of 1:1 (clay:compatibilizer). The influence of different processing conditions (rotation speed and residence time) on the thermal, rheological, and mechanical properties and the interlayer distance was investigated. It was the target to determine whether a short and intensive or a long and soft process performs better. Different properties prefer different states of dispersion of MMT in the polymer matrix. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers  相似文献   

14.
Chen Chen  Donald G. Baird 《Polymer》2012,53(19):4178-4186
The use of supercritical carbon dioxide (scCO2) has proven to be beneficial for surface modified montmorillonite (MMT) nano-clay dispersion up to 6.6 wt% in a polypropylene (PP) matrix and lead to improved material mechanical properties in our earlier research. Our further modifications of the processing procedure including a sequential mixing technique successfully extended the technique to PP composites with as much as 10 wt% of clays and continuously increasing mechanical properties. In order to obtain additional enhancements of the composite properties at this clay level, polypropylene grafted with maleic anhydride (PP-g-MA) is included in this work. The results from the studies of the mechanical properties, rheological properties, and transmission electron microscopy (TEM) show that PP-g-MA is greatly beneficial in generating an exfoliated nano-clay morphology. Greater enhancements in the mechanical properties and nano-clay dispersion in the polymer matrix are observed when PP-g-MA is combined with the scCO2 and sequential mixing techniques. The PP-g-MA based nano-clay composites have a high degree of exfoliated structure even with the addition of up to approximately 10 wt% nano-clay when using this technique, with mechanical properties such as yield strength and Young's modulus being increased by as much as 12 and 88%, respectively, relative to the polymer matrix. It is believed that the modulus reported here is the highest reported in the literature for conventional PP's.  相似文献   

15.
Rajkiran R. Tiwari 《Polymer》2011,52(21):4955-5605
PP/PP-g-MA/MMT/elastomer nanocomposites were prepared in a twin-screw extruder at fixed 30 wt% elastomer and 0-7 wt% MMT content. The ratio of maleated polypropylene, PP-g-MA and organoclay was maintained at 1. Elastomer particle size and shape in the presence of MMT were evaluated for three different molecular weight grades of polypropylene (PP) and five different ethylene-co-octene elastomers (EOR) with different melt flow index (MFI) and octene contents. The MMT particles are located exclusively in the PP phase in the PP/PP-g-MA/MMT/EOR nanocomposites as seen from TEM images. Injection molded nanocomposite samples show significant decreases in elastomer particle size and increases in elastomer aspect ratio and particle density compared to as-extruded or pelletized samples. The elastomer particle size decreased significantly with increased MMT content and the molecular weight of PP. Low molecular weight PP based nanocomposite showed a greater reduction in elastomer particle size compared to medium and high molecular weight PP based nanocomposites. Elastomers having MFI in the range of 0.5-1.0 gave minimum elastomer particle sizes in the PP/PP-g-MA/MMT/EOR nanocomposite. The elastomer particles were deformed during injection molding leading to an increase in their aspect ratio. The nanocomposites containing high octene content elastomer gave smaller elastomer particle size and higher elastomer aspect ratios compared to nanocomposites containing low octene content elastomer.  相似文献   

16.
W. Lertwimolnun 《Polymer》2005,46(10):3462-3471
Polypropylene/organoclay nanocomposites have been prepared via direct melt intercalation in an internal mixer. Maleic anhydride grafted polypropylene (PP-g-MA) was used as a compatibilizer to improve the dispersability of the clay. The structures of nanocomposites have been characterized by X-ray diffraction, transmission electron microscopy and rheometry in small amplitude oscillatory shear. The effects of concentration of PP-g-MA and processing parameters were investigated. Wide angle X-ray diffraction shows that the interlayer spacing increases with the concentration of PP-g-MA, but is not significantly influenced by processing conditions. The study of linear viscoelastic properties shows that the storage modulus G′ is very sensitive to the microstructure of the nanocomposite. A Carreau-Yasuda law with a yield stress is proposed to describe the rheological behavior of these materials. Applications to the twin screw extrusion process are also presented.  相似文献   

17.
The insertion of the aliphatic diamine inside the organoclay will help the dispersion of the clay platelets in the PP/clay nanocomposite due to the reaction between the maleated PP and the diamine. Cloisite®20A was just simply mixed with hexamethylene diamine (HMDA) under shearing condition in Brabender mixer. HMDA group was successfully penetrated into silicate layers. As a result of penetration, d‐spacing of organoclay was increased. Polypropylene/clay nanocomposites were prepared by compounding with maleated PP and amine‐treated clay. From the FTIR spectra, reaction between amine group and maleic‐anhydride group was confirmed. The effect of the organoclay on the properties of the nanocomposite such as the morphology, dynamic mechanical properties, crystal structure and crystallization behavior, glass transition temperature, thermal stability, and tensile properties were investigated and analyzed. Nanocomposites with amine‐treated clays show enhanced properties compared with those with non–amine‐treated clay (Cloisite®20A). From the TEM analysis, nanocomposites with amine‐treated clays shows better dispersibility compared with those with Cloisite®20A alone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

18.
The mechanical and thermomechanical properties as well as microstructures of polypropylene/nylon 6/clay nanocomposites prepared by varying the loading of PP‐MA compatibilizer and organoclay (OMMT) were investigated. The compatibilizer PP‐MA was used to improve the adhesion between the phases of polymers and the dispersion of OMMT in polymer matrix. Improvement of interfacial adhesion between the PP and PA6 phases occurred after the addition of PP‐MA as confirmed by SEM micrographs. Moreover, as shown by the DSC thermograms and XRD results, the degree of crystallinity of PA6 decreased in the presence of PP‐MA. The presence of OMMT increased the tensile modulus as a function of OMMT loading due to the good dispersion of OMMT in the matrix. The insertion of polymer chains between clay platelets was verified by both XRD and TEM techniques. The viscosity of the nanocomposites decreased as PP‐MA loading increased due to the change in sizes of PA6 dispersed phase, and the viscosity increased as OMMT loading increased due to the interaction between the clay platelets and polymer chains. The clay platelets were located at the interface between PP and PA6 as confirmed by both SEM and TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

19.
Polypropylene/organoclay nanocomposites modified with different maleic anhydride grafted polypropylene (PPgMA) compatibilizers were compounded on a twin‐screw extruder. The effectiveness of the feeding sequence and compatibilizer type toward the dispersion of organoclay into PP matrix was critically studied. The composites prepared with side feed appeared to provide better dispersion and modulus improvement over that with hopper feed. The effect of PPgMA compatibilizers, including PB3150, PB3200, PB3000, and E43, with a wide range of maleic anhydride (MA) content and molecular weight was also examined. The structure was investigated with X‐ray diffraction and transmission electron microscopy. The relative complex viscosity curves also revealed a systematic trend with the extent of exfoliation and showed promise for quantifying the hybrid structure of the nanocomposites. Mechanical properties were determined by dynamical mechanical analysis and tensile and impact tests. Maleated polypropylene with low‐melt flow index and moderate MA content enhanced clay dispersion and resulted in significant improvement in tensile modulus of the nanocomposites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 100–112, 2004  相似文献   

20.
Nanocomposites based on polypropylene (PP) and unmodified Montmorillonite were prepared using a novel elaboration route based on a water‐assisted extrusion process. Unmodified Montmorillonite, high shear compounding together with injection of aqueous suspension and reactive processing technology were used. Different aqueous suspensions containing cationic or anionic surfactants, and a compatibilizer (PP‐g‐MA) were injected during extrusion to promote clay dispersion. For a comparison purpose, a commercial PP/clay masterbatch was melt mixed to PP. Structural, morphological, and rheological characterizations indicate clearly that the cationic suspensions ease the dispersion of clay platelets in the PP matrix. No full exfoliation is, however, obtained, and the system remains still less homogeneous than the nanocomposite based on the commercial masterbatch. Nevertheless, mechanical and thermal characterizations of the nanocomposites based on cationic surfactants demonstrate the efficiency to disperse clay in the polymer matrix, and the effect on the ductility compared to usual PP nanocomposites is promising. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers  相似文献   

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