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1.
Mark A. Treece Wei Zhang Ronald D. Moffitt James P. Oberhauser 《Polymer Engineering and Science》2007,47(6):898-911
This work seeks to optimize the twin‐screw compounding of polymer‐clay nanocomposites (PCNs). Proportional amounts (3:1) of maleic anhydride functionalized polypropylene compatibilizer (PP‐g‐MA) and organically modified montmorillonite clay at clay loadings of 1, 3, and 5 wt% were melt‐blended with a polypropylene (PP) homopolymer using a Leistritz Micro 27 twin‐screw extruder. Three melt‐blending approaches were pursued: (1) a masterbatch of PP‐g‐MA and organoclay were blended in one pass followed by dilution with the PP resin in a second pass; (2) all three components were processed in a single pass; and (3) uncompatibilized PP and organoclay were processed twice. Both corotation and counterrotation operation were utilized to investigate the effect of screw rotation mode and sequence on organoclay exfoliation and dispersion. X‐ray diffraction was employed to characterize basal spacing; however, since rheology is known to be highly sensitive to mesoscale organoclay structure, it is an ideal tool to examine the relationship between the various processing methods and exfoliation and dispersion. A holistic analysis of rheological data demonstrates the efficacy of the masterbatch approach, particularly when compatibilizer and organoclay are blended in counterrotating mode followed by dilution with matrix polymer in corotating mode. POLYM. ENG. SCI., 47:898–911, 2007. © 2007 Society of Plastics Engineers 相似文献
2.
Cuneyt Bagcioglu Esra Altuntas Sinan Şen M Bora İslier Osman G Ersoy Nuri Ersoy Turgut Nugay Nihan Nugay 《Polymer International》2008,57(12):1395-1403
BACKGROUND: Both exfoliated and toughened polypropylene‐blend‐montmorillonite (PP/MMT) nanocomposites were prepared by melt extrusion in a twin‐screw extruder. Special attention was paid to the enhancement of clay exfoliation and toughness properties of PP by the introduction of a rubber in the form of compatibilizer toughener: ethylene propylene diene‐based rubber grafted with maleic anhydride (EPDM‐g‐MA). RESULTS: The resultant nanocomposites were characterized using X‐ray diffraction, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, dynamic mechanical analysis and Izod impact testing methods. It was found that the desired exfoliated nanocomposite structure could be achieved for all compatibilizer to organoclay ratios as well as clay loadings. Moreover, a mechanism involving a decreased size of rubber domains surrounded with nanolayers as well as exfoliation of the nanolayers in the PP matrix was found to be responsible for a dramatic increase in impact resistance of the nanocomposites. CONCLUSION: Improved thermal and dynamic mechanical properties of the resultant nanocomposites promise to open the way for highly toughened super PPs via nanocomposite assemblies even with very low degrees of loading. Copyright © 2008 Society of Chemical Industry 相似文献
3.
A wide range of process parameters regulate the final morphology achieved in layered silicate based polymer nanocomposites. This study deals with the optimization of process variables to improve the matrix formulation. A three‐factor, three‐level Box‐Behnken design with compatibilizer concentration (X1), clay concentration (X2), and screw speed (X3) as the independent variables were selected for the study. The dependent variable was mechanical property of the final nanocomposites. Maleic anhydride grafted polypropylene (PP‐g‐MA) compatibilizer and organoclay (Cloisite 15A) was melt blended with polypropylene separately in a corotating twin screw extruder. The clay was modified with fluorescent dye Nile Blue A Perchlorate (NB) and the adsorbed dye content in the clay gallery was estimated by using UV‐spectrophotometric method. The Minitab‐15 software was used for analysis of the results obtained. Optimum compositions for better dispersion were achieved from contour plots and response surface methodology. It was supported by a unique fluorescence spectrophotometry along with transmission electron microscopy and X‐ray diffraction technique. An intensity ratio close to unity showed a better exfoliated morphology. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
4.
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
5.
The Effect of ultra‐high speed twin screw extrusion on ABS/organoclay nanocomposite blend properties
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Azadeh Farahanchi Emily Boehm Nese Orbey Robert Malloy 《Polymer Engineering and Science》2017,57(1):60-68
Acrylonitrile butadiene styrene (ABS) nanocomposites containing Cloisite 11 organoclay at 2 wt% were prepared using a 60 L/D ultra‐ high speed twin screw extruder (TSE), with speeds ranging from 400 to 4000 rpm. The purpose of this study was to investigate the effect of high shear melt processing on the intercalation and exfoliation of organoclay in the polymer, as well as the mechanical and rheological properties of the material. X‐ray Diffraction (XRD), and Transmission Electron Microscopy (TEM) results showed better intercalation of the nanofiller with increasing screw speed up to a point, and indicated an exfoliated structure of the nanocomposites extruded at 4000 rpm. Mechanical and rheological testing results indicated that by adding organoclay to ABS, the properties improved with increasing screw speed up to an optimum value of 2000 rpm. However, at the higher screw speeds of 3000 and 4000 rpm, the intense shear history led to a decrease in properties, most likely due to chain scission and molecular weight reduction. Similar trends were observed in rheological properties of the nanocomposite as well. At 2000 rpm, the results indicate that the lowering of the molecular weight due to shear effects is balanced by good intercalation/exfoliation of the organoclay. POLYM. ENG. SCI., 57:60–68, 2017. © 2016 Society of Plastics Engineers 相似文献
6.
Polypropylene (PP)/organoclay (Cloisite©20A) nanocomposites are prepared via direct melt intercalation in a co‐rotating twin screw extruder. Maleic anhydride (MA)‐grafted PP (PP‐g‐MA) is used as a compatibilizer to improve the dispersion of the clay. The formulation used to prepare the nanocomposites is fixed and is equal to 80/15/5 (PP/PP‐g‐MA/Cloisite©20A), expressed in mass fraction. The objective of the present study is to investigate the effects of processing conditions as well as screw profile upon the formation of PP nanocomposites. The parameters studied are the feed rate and the screw speed, which are varied independently, from 4.5 to 29.0 kg/h and from 100 to 300 rpm, respectively. The state of dispersion is quantified by wide angle X‐ray diffraction (WAXD), transmission electron microscopy, and rheological measurements. WAXD results show that the nanocomposites obtained in different conditions have an intercalated structure, with an increase in interlayer spacing. However, this interlayer spacing is globally unaffected by processing parameters. On the opposite, the proportion of exfoliation, estimated by rheological measurements, is depending on operating conditions (screw speed and feed rate). It increases when the feed rate decreases and the screw speed increases. Investigations on the state of dispersion along the screw profile are also presented. They show that no evolution of intercalated structure is observed along the screws and that screw geometry is only efficient in particular extrusion conditions to delaminate clay platelets. Numerical simulations of the twin screw extrusion process, using the software Ludovic©, put in evidence that the total strain is a key factor for characterizing the level of exfoliation in the nanocomposites. POLYM. ENG. SCI. 46:314–323, 2006. © 2006 Society of Plastics Engineers 相似文献
7.
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
8.
In situ intercalative polycondensation is applied for the preparation of polyamide (PA) n,6–clay nanocomposites, namely poly(ethylene adipamide) (PA 2,6), poly(hexamethylene adipamide) (PA 6,6), and poly(dodecamethylene adipamide) (PA 12,6). For this purpose, two different polymerization routes are considered; a low‐temperature melt polymerization technique and the conventional solution‐melt one. Under the specific experimental conditions, lack of clay exfoliation is detected through XRD measurements, which is proved irreversible even when twin‐screw extrusion is attempted as an additional step. The resulting PA n,6–clay structures are found dependent on the diamine moiety length; more specifically, an intrinsic interaction between the polyamide monomer and the organoclay surfactant is indicated. An ion exchange occurs between the two competitive species, that is, diamine and surfactant cations, leading to flocculated clay structures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
9.
The photo‐oxidation behavior under natural and accelerated conditions of polypropylene/layered silicate nanocomposite is studied in this article. The nanocomposites are prepared via simple melt mixing (extrusion and injection molding). The structure obtained is very dependent on the preparation mode and the modified clay used; mostly, exfoliation structure is produced. The nanocomposites start their photo‐degradation earlier than the control samples polypropylene and polypropylene‐graft‐maleic anhydride with a higher oxidation rate for specimen produced by injection molding. This is explained by the presence of organiphilic‐modified montmorillonite layers that trap the oxygen, increasing the oxygen pressure in the bulk and leading to a decrease of the induction period. Contrary to the control samples that display auto acceleration in their oxidation kinetics, the nanocomposites show a slight tendency to a plateau indicating a slowing down of the photo‐oxidation process. This is ascribed to oxygen starvation that occurs in the nanocomposite. The acceleration factor is found to be higher for the nanocomposite comparatively of the control samples. With the aid of SF4 and NO treatments, the mechanism of photo degradation was found to be similar in PPgMA and its nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 相似文献
10.
Philip J. Brunner Joshua T. Clark John M. Torkelson Katsuyuki Wakabayashi 《Polymer Engineering and Science》2012,52(7):1555-1564
Solid‐state shear pulverization (SSSP) is a unique processing technique for mechanochemical modification of polymers, compatibilization of polymer blends, and exfoliation and dispersion of fillers in polymer nanocomposites. A systematic parametric study of the SSSP technique is conducted to elucidate the detailed mechanism of the process and establish the basis for a range of current and future operation scenarios. Using neat, single component polypropylene (PP) as the model material, we varied machine type, screw design, and feed rate to achieve a range of shear and compression applied to the material, which can be quantified through specific energy input (Ep). As a universal processing variable, Ep reflects the level of chain scission occurring in the material, which correlates well to the extent of the physical property changes of the processed PP. Additionally, we compared the operating cost estimates of SSSP and conventional twin screw extrusion to determine the practical viability of SSSP. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers 相似文献
11.
Long‐chain branching polypropylene (LCB‐PP)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder. The microstructure and melt rheology of these nanocomposites were investigated using x‐ray diffraction, transmission electron microscopy, oscillatory shear rheology, and melt elongation testing. The results show that, the clay layers are intercalated by polymer molecular chains and exfoliate well in LCB‐PP matrix in the presence of maleic anhydride grafted PP. Rheological characteristics, such as higher storage modulus at low‐frequency and solid‐like plateau in tan‐ω curve, indicate that a compact and stable filler network structure is formed when clay is loaded at 4 phr (parts per hundred parts of) or higher. The response of the nanocomposite under melt extension reveals an initial decrease in the melt strength and elongational viscosity with increasing clay concentration up to 6 phr. Later, the melt strength and elongational viscosity show slight increases with further increasing clay concentration. These results might be caused by a reduction in the molecular weight of the LCB‐PP matrix and by the intercalation of LCB‐PP molecular chains into the clay layers. Increases in the melt strength and elongational viscosity for the nanocomposites with decreasing extrusion temperature are also observed, which is due to flow‐induced crystallization under lower extrusion temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
12.
A. L. F. de M. Giraldi M. T. M. Bizarria A. A. Silva J. I. Velasco Marcos A. d'Ávila L. H. I. Mei 《应用聚合物科学杂志》2008,108(4):2252-2259
The effects of extrusion conditions on the mechanical properties of recycled poly(ethylene terephthalate) (rPET)/clay nanocomposites were studied. Nanocomposites of recycled PET containing 2.5 and 5.0 wt % of montmorillonite modified with organophilic quaternary ammonium salt (DELLITE 67G) were prepared by melt compounding using a corotating twin‐screw type extruder at two different screw rotation speeds: 250 and 150 rpm. The highest value of Young's modulus was found for low screw rotation speed (150 rpm). Morphological analysis using transmission electron microscopy (TEM) revealed the presence of fully exfoliated clay platelets in samples prepared at 150 rpm. It was concluded that the screw rotation speed should be optimized when preparing recycled PET/clay nanocomposites by melt compounding. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
13.
Polymer blends of carboxylated butadiene‐acrylonitrile copolymer (nitrile rubber) and polyamide 6 (PA6) were developed in twin screw extrusion. The rubber was cured with SP 1045 methylol phenolic resin during melt mixing in twin screw. Effect of degree of carboxylation in the rubber phase on blend properties has been assessed. Phase morphologies have been characterized using transmission electron microscopy. A compatibilizing NBR‐g‐Nylon 6 graft copolymer generated in situ during melt mixing via interfacial reaction between the ? COOH groups in NBR and the ? NH2 end groups in nylon 6 has been effective in generating a fine and stable dispersion of the rubber within the polyamide matrix. The graft copolymer has been characterized by DMTA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 372–377, 2007 相似文献
14.
This study focuses on the degree of dispersion and structural development of organomodified MMT clay (OMMT) during processing of polypropylene clay nanocomposites using both conventional and nonconventional characterization techniques. PP‐g‐MA and Cloisite 15A were melt blended with three different grades of PP separately in a micro‐twin screw compounder at selected screw speed and temperature. The clay was modified with fluorescent dyes and the adsorbed dye content in the clay gallery was estimated by using UV‐spectrophotometric method. The effects of residence time and molecular weight of the PP matrix on the clay dispersion were studied. The extent of dispersion and exfoliation of the clay in polymer matrix determined from the torque versus time data obtained from microcompounder. It was further supported by XRD, SEM, TEM, and DSC analysis. Offline dielectric and fluorescence spectrophotometric studies were also carried out. Changes in dielectric constant and dielectric loss with both frequency and temperature yielded quantitative information about the extent of clay exfoliation and intercalation in the polymer matrix. It was observed that with an increase in MFI (decrease in molecular weight) and mixing time, the extent of clay dispersion and exfoliation were also improved due to easy diffusion of polymer chains inside clay gallery. POLYM. COMPOS., 31:2007–2016, 2010. © 2010 Society of Plastics Engineers 相似文献
15.
Shuichi Tanoue Aniwat Hasook Takumi Itoh Masaharu Yanou Yoshiyuki Iemoto Tsunemune Unryu 《应用聚合物科学杂志》2006,101(2):1165-1173
We discuss the effect of screw rotation speed on the mechanical and rheological properties and clay dispersion state of polystyrene (PS)/organoclay (clay) nanocomposites prepared by melt compounding with a counterrotating‐type twin‐screw extruder. Poly(styrene‐co‐vinyloxazolin) (OPS) was used as an additional material. The Young's modulus of the PS/OPS/clay nanocomposites showed the maximum value at a screw rotation speed of 70 rpm in this study. This implied the existence of an optimized screw rotation speed for the melt compounding of the polymer/clay nanocomposites. For PS/clay systems without the addition of OPS, the peak intensity from clay increased and the distance between clay platelets in the nanocomposites decreased with the screw rotation speed. On the other hand, inverse results were obtained for PS/OPS/clay systems. According to the transmission electron microscopy photographs, the PS/OPS/clay nanocomposite at 70 and 100 rpm had fully exfoliated clay platelets. The dynamic rheological properties of the PS/clay nanocomposites were almost the same as those of neat PS. On the other hand, the storage and loss moduli of the PS/OPS/clay nanocomposites at the same frequency were larger than those of the PS/clay system. On the whole, the bonding between clay platelets and PS was important for increasing the viscosity and elasticity in the melts of the PS/clay system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1165–1173, 2006 相似文献
16.
M. Aloui J. Soulestin M.‐F. Lacrampe P. Krawczak D. Rousseaux J. Marchand‐Brynaert J. Devaux N. Quiévy M. Sclavons 《Polymer Engineering and Science》2009,49(11):2276-2285
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
17.
Polymer melt‐direct intercalation or exfoliation is a promising approach for the preparation of nanocomposites. The structure of nanoclay platelets in the nanocomposites depends not only on the properties of polymer matrix and nanoclay, but also on the operating conditions during processing. The objective of the present work is to investigate the effects of clay chemical modifiers, mixing protocols, and operating conditions upon the clay structure in nanocomposites prepared with a corotating twin‐screw extruder. Two mixing methods were used for the nanocomposite preparation: two‐step mixing and one‐step mixing. Experimental results obtained from melt flow index and complex viscosity measurements suggest that nanoclay C15A is more exfoliated than C30B in a polypropylene homopolymer containing a maleic anhydride grafted PP (PB) as compatibilizer. The two‐step mixing method results in better exfoliation for the nanofillers than the one‐step mixing method. A numerical simulation has been carried out to evaluate the mean residence time and shear rate in different screw configurations under various process conditions. X‐ray diffraction experiments indicate that the residence time is a dominant factor in producing satisfactory nanocomposites in extruders. However, high shear rate coupled with long residence time might result in poor exfoliation of clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1891–1899, 2004 相似文献
18.
Saddys Rodríguez‐Llamazares Bernabé L. Rivas Mónica Pérez Florence Perrin‐Sarazin Alvaro Maldonado Carola Venegas 《应用聚合物科学杂志》2011,122(3):2013-2025
Clay containing polypropylene (PP) nanocomposites were prepared by direct melt mixing in a twin screw extruder using different types of organo‐modified montmorillonite (Cloisite 15 and Cloisite 20) and two masterbatch products, one based on pre‐exfoliated clays (Nanofil SE 3000) and another one based on clay–polyolefin resin (Nanomax‐PP). Maleic anhydride‐grafted polypropylene (PP‐g‐MA) was used as a coupling agent to improve the dispersability of organo‐modified clays. The effect of clay type and clay–masterbatch product on the clay exfoliation and nanocomposite properties was investigated. The effect of PP‐g‐MA concentration was also considered. Composite morphologies were characterized by X‐ray diffraction (XRD), field emission gun scanning electron microscopy (FEG‐SEM), and transmission electron microscopy (TEM). The degree of dispersion of organo‐modified clay increased with the PP‐g‐MA content. The thermal and mechanical properties were not affected by organo‐modified clay type, although the masterbatch products did have a significant influence on thermal and mechanical properties of nanocomposites. Intercalation/exfoliation was not achieved in the Nanofil SE 3000 composite. This masterbatch product has intercalants, whose initial decomposition temperature is lower than the processing temperature (T ~ 180°C), indicating that their stability decreased during the process. The Nanomax‐PP composite showed higher thermal and flexural properties than pure PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
19.
Jr Hao Liaw Tony Yi Hsueh Tai‐Sheng Tan Yeh Wang Shu‐Min Chiao 《Polymer International》2007,56(8):1045-1052
Poly(methyl methacrylate) (PMMA)/organoclay nanocomposites prepared by melt‐compounding using a co‐rotating twin‐screw extruder were intercalated nanocomposites. Commercially available PMMA resins of various molecular weights were used for comparison. The results showed an optimum compounding temperature for maximum intercalation with balanced shear and diffusion. Higher operating temperature reduced the shear mixing effect, and might have induced early degradation of the organoclay. Lower operating temperature, in contrast, reduced the mobility of the polymer molecules, which not only hampered the intercalation attempts, but also generated high torque in the extrusion. The mechanical behavior of the nanocomposites was studied. The tensile modulus, storage modulus and glass transition temperature of the nanocomposites increased with increasing clay content; however, an associated decrease in strength and strain at break was also observed. The notched impact strength also showed a slight decrease with clay content. Nanocomposites based on the lower molecular weight PMMA yielded more significant improvement in mechanical and thermal properties at the same clay content. Copyright © 2007 Society of Chemical Industry 相似文献
20.
Poly(ethylene‐co‐vinyl acetate) (EVA) and organophilic montmorillonite clay nanocomposites were manufactured in a co‐rotating twin‐screw extruder using screw speeds ranging between 200 and 800 rpm. The morphology and thermal‐mechanical and rheological properties were studied to establish processing–morphology–property relationships. Particularly for samples produced under higher screw speed ranges, X‐ray diffraction and transmission electron microscopy revealed a tendency of increased exfoliated clay. Although the mechanical properties improved by the presence of clay, they were not altered by the screw speed. The rheological behavior in the solid and melt states were evaluated and showed that the storage modulus of neat EVA subjected to higher screw speed undergoes more pronounced decrease in the storage modulus than the nanocomposites, suggesting that the clay minimizes the effect of the screw speed. This minimization effect could be explained in the light of the assessment of relaxation times that showed stronger physical interactions with the nanocomposites in the molten state. POLYM. COMPOS., 36:854–860, 2015. © 2014 Society of Plastics Engineers 相似文献