Morphology and properties of SAN‐clay nanocomposites prepared principally by water‐assisted extrusion

An efficient extrusion process involving the injection of water while processing was used to prepare poly (styrene‐co‐acrylonitrile) (SAN)/clay nanocomposites with a high degree of nanoclay delamination. The usefulness of water‐assisted extrusion is highlighted here, in comparison with classical extrusion and roll mill processes. Cloisite® 30B (C30B), a montmorillonite clay organomodified with alkylammonium cations bearing 2‐hydroxyethyl chains, and pristine montmorillonite were melt blended with SAN (25 wt% AN) in a semi‐industrial scale extruder specially designed to allow water injection. XRD analysis, visual and TEM observations were used to evaluate the quality of clay dispersion. The relationship between the nanocomposite morphology and its mechanical and thermal properties was then investigated. The superiority of the SAN/C30B nanocomposite extruded with water has been evidenced by cone calorimetry tests and thermogravimetric measurements (TGA). These analyses showed a substantial improvement of the fire behavior and the thermal properties, while a 20% increase of the Young modulus was recorded. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Microstructure and properties of poly(ethylene terephthalate)/organoclay nanocomposites prepared by water‐assisted extrusion: Effect of organoclay concentration

Poly(ethylene terephthalate) (PET)/Cloisite 30B (C30B) nanocomposites containing different concentrations of the organoclay were prepared using two different twin‐screw extrusion processes: conventional melt mixing and water‐assisted melt mixing. The reduction of the molecular weight of the PET matrix, caused by hydrolysis during the water‐assisted extrusion, was compensated by subsequent solid‐state polymerization (SSP). X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses showed intercalated/exfoliated morphology in all PET/C30B nanocomposites, with a higher degree of intercalation and delamination for the water‐assisted process. Rheological, thermal, mechanical, and gas barrier properties of the PET nanocomposites were also studied. Enhanced mechanical and barrier properties were obtained in PET‐C30B nanocomposites compared to the neat PET. The nanocomposites exhibited higher tensile modulus and lower oxygen permeability after SSP. The elongation at break was significantly higher for SSP nanocomposites than for nanocomposites processed by conventional melt mixing. POLYM. ENG. SCI., 54:1879–1892, 2014. © 2013 Society of Plastics Engineers     

Effect of water‐assisted extrusion and solid‐state polymerization on the microstructure of PET/Clay nanocomposites

An melt‐mixing process has been used to prepare Poly(ethylene terephthalate) (PET)/clay nanocomposites with high degree of clay delamination. In this method, steam was fed into a twin‐screw extruder (TSE) to reduce the PET molecular weight and to facilitate their diffusion into the gallery spacing of organoclays. Subsequently, the molecular weight (M_W) reduction of the PET matrix due to hydrolysis by water was compensated by solid‐state polymerization (SSP). The effect of the thermodynamic compatibility of PET and organoclays on the exfoliated microstructure of the nanocomposites was also examined by using three different nanoclays. The dispersion of Cloisite 30B (C30B) in PET was found to be better than that of Nanomer I.28E (I28E) and Cloisite Na⁺. The effect of feeding rate and consequently residence time on the properties of PET nanocomposites was also investigated. The results reveal more delamination of organoclay platelets in PET‐C30B nanocomposites processed at low feeding rate compared to those processed at high feeding rate. Enhanced mechanical and barrier properties were observed in PET nanocomposites after SSP compared to the nanocomposites prepared by conventional melt‐mixing. POLYM. ENG. SCI., 54:1723–1736, 2014. © 2013 Society of Plastics Engineers     

A high‐barrier PP/EVOH membrane prepared through the multistage biaxial‐stretching extrusion

The polypropylene (PP)/ethylene vinyl alcohol copolymer (EVOH) membranes were prepared by a novel extrusion die with an assembly of laminating‐multiplying elements (LMEs). A biaxial‐stretching occurred when polymer melts flowing through a LME. The morphology development of PP/EVOH blends and its effect on gas‐barrier property, solvent‐absorption property and mechanical properties were characterized by scanning electron microscope (SEM), polarized optical microscope (POM), gas‐permeability test, immersion experiment, differential scanning calorimetry (DSC), and tensile test. With the introduction of LME and the increasing of its number, morphology of EVOH phase in PP matrix gradually changed from zero‐dimension spherical particles to one‐dimension fibers, and then to two‐dimension sheets. As a result, the nitrogen permeability coefficient decreased nearly by two orders of magnitude and the permeability coefficient of toluene‐PP/EVOH system declined by almost four times. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45016.     

Properties of polyetherimide/graphite composites prepared using ultrasonic twin‐screw extrusion

The dispersion of various graphites in polymers is a challenging problem limiting their potential use. To solve this problem, an ultrasound assisted twin‐screw extruder was developed and utilized to compound polyetherimide (PEI) with untreated nature graphite (UG), modified graphite (MG) and expanded graphite (EG) at concentrations up to 10 wt %. The effect of ultrasonic amplitude on rheological, mechanical and electrical properties of the PEI composites was investigated. Ultrasonic treatment of PEI/UG composites showed little effect on these properties. In contrast, ultrasonic treatment of PEI/MG and PEI/EG composites led to an increase of the storage (G′), loss (G″) moduli and complex viscosity and to a decrease of the damping characteristics. In particular, the PEI/5 wt %EG composite ultrasonically treated at an amplitude of 10 μm showed a 45% higher complex viscosity than the untreated composite at a frequency of 0.5 rad/s. Also, the PEI/5 wt % EG composite treated at an amplitude of 10 μm showed a reduction in the electrical volume resistivity by almost three orders of magnitude leading to a lower percolation threshold. The untreated and treated PEI/UG and PEI/MG composites did not show any percolation within all graphite concentrations studied, due to large size of particles of UG and MG and their strong agglomeration. The ultrasonic treatment showed slight effect on mechanical properties of all these composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41397.     

Multiscale fiber‐reinforced composites prepared by vacuum‐assisted resin transfer molding

Carbon nanotube (CNT)/aramid fiber epoxy composites were produced using a new manufacturing method proposed in this study. The rheological and morphological experiments of the CNT/PEO nanocomposites indicates that the PEO nanocomposites have a good dispersion state of the CNTs. The flexural mechanical properties of the aramid fiber/CNT epoxy composites were measured. The CNTs dispersed in the epoxy resin between the aramid fibers were observed using field emission scanning electron miscroscope (FESEM). It was found that the flexural properties of the multiscale fiber‐reinforced composites were higher than those of aramid fiber/epoxy composites. POLYM. COMPOS., 28:458–461, 2007. © 2007 Society of Plastics Engineers.     

Viscoelastic behavior of epoxy/carbon fiber/Zno nano‐rods hybrid composites

The insufficient viscoelastic resistance of fiber reinforced plastics can be retrofitted by the addition of more rigid nano fillers to the polymer matrix. In this study, carbon fibers plies were grafted with zinc oxide (ZnO) nano‐rods and the hybridized reinforcement was utilized in laminated composites. Flexural creep tests were carried out using dynamic mechanical analysis (DMA) and the time/temperature superposition principle was employed for accelerated testing. To verify the applicability of TTPS, prolonged stress relaxation tests were also carried out in flexural mode. Data from the DMA flexural creep tests revealed that the whiskerization of carbon fibers with ZnO nano rods reduced the creep compliance by 23% at elevated temperatures and prolonged durations. Also, the relaxation data confirmed the applicability of TTPS to these hybrid composites. The stress relaxation modulus improved by 65% in comparison to composites based on neat carbon fibers. POLYM. COMPOS., 36:1967–1972, 2015. © 2014 Society of Plastics Engineer     

Mechanical properties,water‐swelling behavior,and morphology of water‐swellable rubber prepared using crosslinked sodium polyacrylate

A novel water‐swellable rubber (WSR) has been prepared by blending chlorobutadiene rubber (CR), reactive clay and other additives with crosslinked sodium polyacrylate (CSP), which was modified by interpenetrating polymer networks (IPNs) technology with crosslinked P(AA‐co‐BA). The structure of WSR was characterized by scanning electron microscopy (SEM). The mechanical properties, water‐swelling ratio by mass, and the percentage loss of CSP in the WSR were investigated. The results showed that the modified CSP grains can be dispersed well in the CR, and that it resulted in increase of mechanical properties and water‐swelling ratio and in decrease of percentage loss of CSP, compared with the unmodified one. When the percentage content of crosslinked P(AA‐co‐BA) used to modify CSP reached 30%, the tensile strength, elongation at break, and water‐swelling ratio of WSR exhibited maximum value, and percentage loss of CSP exhibited minimum value. When the content of CSP in WSR was 30 phr, the tensile strength, elongation at break, and water‐swelling ratio and percentage loss of CSP of the WSR containing CSP modified were 7.7 MPa, 1530, 438, and 2.5%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1489–1496, 2006     

Study of dynamically cured PP/MAH‐g‐PP/talc/epoxy composites

In the present study, an epoxy resin was dynamically cured in a polypropylene (PP)/maleic anhydride–grafted PP (MAH‐g‐PP)/talc matrix to prepare dynamically cured PP/MAH‐g‐PP/talc/epoxy composites. An increase in the torque at equilibrium showed that epoxy resin in the PP/MAH‐g‐PP/talc composites had been cured by 2‐ethylene‐4‐methane‐imidazole. Scanning electron microscopy analysis showed that MAH‐g‐PP and an epoxy resin had effectively increased the interaction adhesion between PP and the talc in the PP/talc composites. Dynamic curing of the epoxy resin further increased the interaction adhesion. The dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had higher crystallization peaks than did the PP/talc composites. Thermogravimetric analysis showed that the addition of MAH‐g‐PP and the epoxy resin into the PP/talc composites caused an obvious improvement in the thermal stability. The dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had the best thermal stability of all the PP/talc composites. The PP/MAH‐g‐PP/talc/epoxy composites had better mechanical properties than did the PP/MAH‐g‐PP/talc composites, and the dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had the best mechanical properties of all the PP/talc composites, which can be attributed to the better interaction adhesion between the PP and the talc. The suitable content of epoxy resin in the composites was about 5 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Relations between structure and property of polyamide 11 nanocomposites based on raw clays elaborated by water‐assisted extrusion

Bio‐based polymers and polymer nanocomposites have known an increasing interest during the past few years. This work is focused on the elaboration and the characterization of bio‐based nanocomposites made from polyamide 11 (PA11) and nonorganomodified montmorillonite. To elaborate these materials an original elaboration process, consisting in injecting water during the extrusion, was used. Results show that thanks to this process, a well exfoliated morphology is obtained for clay contents as high as 10% wt. This was explained on the one hand by the fact that the clay is soluble in water and on the other hand by the fact that water and PA11 are miscible at high pressure and high temperature. Moreover, the morphology analyses have revealed that from 10% wt of clay, the platelets were not totally randomly distributed but they were rather organized at a mesoscopic scale. The obtaining of such clay's dispersion involves an enhancement of thermomechanical properties. For example, for a clay content of 10% wt, the Young's modulus of the material can be doubled and its degradation temperature increased. The role of the elaboration conditions on the morphology and subsequent properties of the nanocomposites are also carefully analyzed. Finally, it has been evidenced that the presence of the filler infers on both the crystalline form induced and the crystallization kinetics. In summary, this study demonstrates that, in the case of PA11 nanocomposites, the water‐assisted injection process leads to the achievement of an exfoliated morphology for clay contents as high as 10% wt that allows to obtain high performance materials and to be free from using organomodified clays. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improved processing behaviors and mechanical properties of polyolefin elastomer blends prepared by ultrasound‐assisted extrusion

To improve the processability of ethylene‐α‐olefin copolymers (POE), POE and POE/polystyrene (PS) blends were extruded in the presence of ultrasound. On the one hand, the effect of ultrasound on the die pressure drop, extrudate productivity, melt viscosity of POE, and the processing behaviors of POE and POE/PS (80/20) blend were studied. The results showed that with increasing ultrasound power, the die pressure and melt‐apparent viscosity of POE decreased whereas the productivity of POE extrudates increased, then the processability of POE was greatly improved. On the other hand, the effects of ultrasound on the morphology, rheological, and mechanical properties of POE/PS (80/20) blend were studied. Capillary rheological results showed that the merger of ultrasound and the addition of PS showed a synergistic improvement of processability of POE. From morphological observation and rheological analysis, the compatibility of the blend was also improved in the presence of 200W ultrasound. As a result, the stress at break of compatibilized POE/PS (80/20) blend increased from 9.2 to 11.0 MPa, and the dynamic storage modulus increased at experimental temperature range, indicating that the mechanical properties of POE/PS blends can be improved by ultrasound‐assisted extrusion. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Impact behavior of sawdust/recycled–PP composites

The instrumented Izod and Charpy tests were performed on the sawdust–polypropylene (PP) composites to study the nature of impact resistance in the thermoplastic wood composites. The notched Izod strength was found to increase with filler content in composites containing the Maleic–anhydride–grafted PP (MAPP) additive. The Izod strength even exceeds that of the neat matrix resin at higher filler contents, indicating a methodology for applying the recycled PP and also for reinforcing the thermoplastics with wood powders. While the static tensile results show evidences for the reinforcing role of the wood filler, a fracture mechanics characterization through the Charpy impact tests effects of MAPP under the impact loading rates. The choice of MAPP as the additive was discussed accordingly for application of the sort of materials. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1420–1428, 2001     

Viscoelastic properties of polypropylene/organo‐clay nano‐composites prepared using miniature lab mixing extruder from masterbatch

Polypropylene (PP) was melt blended with nano organo‐clay masterbatch at different ratios; namely 5, 10, and 15 wt % of nano‐clay. The effect of organo‐clay content on the viscoelastic properties of the nano‐composite was studied. A miniature laboratory mixing extruder, LME, was used to blend the nano organo‐clay masterbatch with PP at 260°C and 250 rpm. The blend was pelletized first, and then a thin ribbon was extruded. Two viscoelastic tests were performed; frequency sweep at constant temperature of 80°C, and temperature sweep at constant frequency of 1.0 rad/s. As the loading of nano‐clay increased, the storage modulus, G', and the thermal resistance increased as well. Different viscoelastic models were tried and 3‐elements Maxwell model was found to describe well the viscoelastic properties of the nano‐composites. The ratio of the complex modulus to the corresponding matrix modulus at different frequencies was found to vary proportional to the nanoclay loading. This dependency was described reasonably well by modified Guth model using particle aspect ratio of 12.1. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ultrasonic treatment of PP/CNT composites during twin‐screw extrusion: Effect of screw configuration

PP/CNT composites were prepared by means of an ultrasonic twin extruder with three screw configurations at ultrasonic amplitudes up to 13 μm to compare their efficiency in dispersing CNT in PP. Using these screw configurations, the pressure in the ultrasonic treatment zone was varied in order to elucidate the effect of pressure on ultrasonic cavitation behavior in PP and PP/CNT composites. Rheological and mechanical behaviors were analyzed to reflect the dispersion of CNT. The results indicated that the dispersion of CNT in PP is more related to the number of kneading elements in the screw configuration and less to the residence time. This was explained by simulating the mixing effect using the flow analysis network. Comparison of the complex viscosities of untreated and treated PP indicated that at the same amplitude of ultrasonic treatment, PP degraded more at lower ambient pressure. At the lowest ambient pressure, the cavitation in the polymer matrix was intense at the highest amplitude but it had not always led to the best dispersion due to the suppression of the cavitation in the agglomerates. Therefore, the ultrasonic treatment increased the dispersion level of CNT in PP with the best improvement not always occurring at the highest amplitude. Composites prepared at an ultrasonic amplitude of 10 μm in the screw configuration providing an intermediate pressure exhibited elongation at break as high as 320% compared to 247% for the untreated composites. POLYM. COMPOS., 38:2695–2706, 2017. © 2015 Society of Plastics Engineers     

Solvent‐assisted extrusion of polypropylene/clay nanocomposites

Polypropylene (PP) nanocomposites were prepared by a melting‐compounding process with a montmorillonite (MMT) suspension. In this process, an organically modified MMT was swollen in a polar solvent and blended with molten PP in an extruder; this was followed by solvent removal. The effect of a coswelling agent was also evaluated. The nanocomposites were characterized with X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and scanning electron microscopy. In addition, the mechanical properties of the materials were studied. The nanocomposites prepared with the clay suspension presented a remarkable increase in the impact strength with the maintenance of their flexural modulus. The mechanical properties of the nanocomposites were found to be related to the interaction between PP and the clay. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tribological behavior of short‐fiber‐reinforced polyimide composites under dry‐sliding and water‐lubricated conditions

Polyimide composites reinforced with short‐cut fibers such as carbon, glass, and quartz fibers were fabricated by the polymerization of monomer reactants process. The mechanical properties of the composites with different fiber contents were evaluated. The friction and wear properties of the polyimide and its composites were investigated under dry‐sliding and water‐lubricated conditions. The results indicated that the short‐carbon‐fiber‐reinforced polyimide composites had better tensile and flexural strengths and improved tribological properties in comparison with glass‐fiber‐ and quartz‐fiber‐reinforced polyimide composites. The incorporation of short carbon fibers into the polyimide contributed to decreases in the friction coefficient and wear rate under both dry and water‐lubricated conditions and especially under water lubrication because of the boundary lubrication effect of water. The polyimide and its composites were characterized by plastic deformation, microcracking, and spalling under both dry and water‐lubricated conditions, which were significantly abated under the water‐lubricated condition. The glass and quartz fibers were easily abraded and broken; the broken fibers transferred to the mating metal surface and increased the surface roughness of mating stainless steel, which led to the wear rate increasing for the glass‐fiber‐ and quartz‐fiber‐reinforced polyimide composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

反应降解聚丙烯的高速挤出流动稳定性

采用双毛细管流变仪研究了反应降解聚丙烯试样的挤出稳定性。结果表明:基础树脂聚丙烯PP-2401的挤出压力随剪切速率增高呈阶梯状稳定增高,而降解聚丙烯的挤出压力随剪切速率增高出现不规则波动;低相对分子质量降解聚丙烯的压力波动主要发生在口模入口区;发生波动的原因与聚丙烯分子链结构特征有关,同时与熔体在口模区的Weissenberg准数和Reynolds准数较大有关。     

Synthesis and characterization of water‐soluble polypyrrole/multi‐walled carbon nanotube composites

Water‐soluble polypyrrole (PPy)/multi‐walled carbon nanotube (MWCNT) composites were prepared by mixing chemically modified MWCNTs carrying carboxylic groups (c‐MWCNTs) and sulfonated PPy (SPPy) aqueous colloids in solution. Fourier transform infrared spectroscopy, Raman spectroscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, field‐emission scanning electron microscopy and high‐resolution transmission electron microscopy were used to characterize the structure and morphology of the resulting composites. Raman and X‐ray photoelectron spectra demonstrate the presence of electrostatic interactions between the radical species of the SPPy and the carboxylic acid species of the c‐MWCNTs. The addition of c‐MWCNTs into SPPy efficiently enhances its thermal stability and electrical conductivity. Owing to the doping effect and one‐dimensional linear structure of the c‐MWCNTs, the conductivity of SPPy/c‐MWCNT composites at room temperature is increased by two orders of magnitude by the introduction of 5 wt% c‐MWCNTs into the SPPy matrix. Copyright © 2010 Society of Chemical Industry     

Nonisothermal crystallization of PP/nano‐SiO2 composites

The kinetics of nonisothermal crystallization of polypropylene (PP) containing nanoparticles of silicon dioxide (SiO₂) were investigated by differential scanning calorimetry (DSC) at various cooling rates. Several different analysis methods were used to describe the process of nonisothermal crystallization. The results showed that the Ozawa equation and Mo's treatment could describe the nonisothermal crystallization of the composites very well. The nano‐SiO₂ particles have a remarkable heterogeneous nucleation effect in the PP matrix. The rate of crystallization of PP/nano‐SiO₂ is higher than that of pure PP. By using a method proposed by Kissinger, activation energies have been evaluated to be 262.1, 226.5, 249.5, and 250.1 kJ/mol for nonisothermal crystallization of pure PP and PP/nano‐SiO₂ composites with various SiO₂ loadings of 1, 3, and 5%, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1013–1019, 2004