Compatibilization level effects on the structure and mechanical properties of rubber‐modified polyamide‐6/clay nanocomposites

Exfoliated polyamide‐6 (PA6)/organically modified montmorillonite clay (OMMT) nanocomposites (PNs) were modified with partially maleinized styrene–ethylene/butadiene–styrene triblock copolymers (SEBS) at three maleinization levels in an attempt to link in these materials high toughness with appropriate small‐strain and fracture tensile properties. OMMT stayed only in the PA6 matrix, and no preferential location in the matrix/rubber interphase was observed. The increased dispersed phase size upon the addition of OMMT was attributed to interactions between maleic anhydride (MA) functionalized SEBS and the surfactant of OMMT. The rubber particle size generally decreased when the MA content of SEBS increased, and this indicated compatibilization. The subsequent good adhesion led to tough nanocomposites across a wide range of both strain rates and fracture modes. As the critical interparticle distance (τ_c) decreased with the MA content, and the other parameters that could influence the surface‐to‐surface mean interparticle distance did not change, it is proposed that in these PNs higher adhesion leads to a smaller τ_c value. Finally, the presence in the matrix of a nanostructured clay makes the rubber content necessary for the toughness jump to increase and τ_c to decrease. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3611–3620, 2005     

Effect of surface modification of montmorillonite on the properties of aromatic polyamide/clay nanocomposites

The surface modification of montmorillonite clay was carried out through ion‐ exchange reaction using p‐phenylenediamine as a modifier. This modified clay was employed to prepare aromatic polyamide/organoclay nanocomposite materials. The dispersion behavior of clay was examined in the polyamide matrix. Polyamide chains were synthesized from 4‐aminophenyl sulfone and isophthaloyl chloride (IPC) in dimethylacetamide. These amide chains were suitably end‐capped with carbonyl chloride end groups to interact chemically with modified montmorillonite clay. The resulting nanocomposite films containing 2–20 wt% of organoclay were characterized by TEM, X‐ray diffraction (XRD), thin‐film tensile testing; thermogravimetric analysis (TGA), differential scanning calorimetric (DSC) and water absorption measurements. Mechanical testing revealed that modulus and strength improved up to 6 wt% organoclay loading while elongation and toughness of nanocomposites decreased with the addition of clay content in the matrix. Thermal decomposition temperatures of the nanocomposites were in the range 225–450 °C. These nanocomposites expressed increase in the glass‐transition temperature values relative to pure polyamide describing interfacial interactions among the phases. The percent water uptake of these composites reduced upon the addition of modified layered silicate depicting improved barrier properties. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of fulleroid materials on the mechanical and tribological properties and dielectric relaxation of polyamide 6 nanocomposites

The effect of fulleroid materials (fullerene С₆₀ and fullerene soot, which is used for fullerenes production) on the mechanical and tribological properties of polymer nanocomposites based on polyamide 6 (PA6) was investigated. Composites were synthesized by direct mixing in an extruder. The use of the nanoparticles was an effective way to decrease the friction coefficient of the polymer composites because the fillers had the same size as the segments of the surrounding polymer chains. The steady state coefficients of friction with addition of fulleroid fillers were lower than that of unfilled PA6. The lowest coefficient of friction was observed for PA6 filled with 1 wt% fullerene soot. Dielectric spectroscopy was used to investigate the influence of nanoparticles on the relaxation processes in the polymer matrix. It is found that the segmental relaxation processes become faster with the addition of fullerene С₆₀. In contrast, the secondary processes of PA6/fullerene C₆₀ nanocomposites were observed to slow down with the addition of fullerene C₆₀. This means that the local “molecular stiffness” is increased, and a phenomenological link between the secondary relaxation times and the mechanical properties explains the increase in the Young's modules of the nanocomposites upon the addition of С₆₀. These observations suggest that nanoparticles can have a qualitatively different effect on the matrix polymer dynamics at different length scales, and caution must be taken in comparing the changes in the dynamics associated with different relaxation processes. Copyright © 2016 John Wiley & Sons, Ltd.     

Influence of preparation methods on the structures and properties for the blends between polyamide 6co6T and polyamide 6: Melt‐mixing and in‐situ blending

Two blends between polyamide 6 (PA6) and Polyamide 6co6T (PA6co6T, a random copolymer between polyamide 6 and polyamide 6T) were fabricated by melt‐mixing on a twin‐screw extruder and the subsequent injection molding, or through the in‐situ polymerization of ε‐caprolactam in the presence of PA6co6T. As far as the former method is concerned, there exist an obvious decline of toughness and a slight increase in strength and modulus; however, for the latter, there appear a remarkable improvement in toughness and a simultaneous moderate increase in strength and modulus. A series of characterizations were carried out including scanning electron microscopy, wide‐angle X‐ray diffraction, polarized optical microscopy, differential scanning calorimetry, dynamic mechanical analysis, and Fourier transform infrared spectrometry. It is found that both blends exhibit single glass transition on DMA tan δ curves. However, contrary to that of the melt‐mixed blends, the glass transition temperature (T_g) of the in‐situ ones decreases with increasing PA6co6T content. It is suggested that different mixing levels are the main reasons. Moreover, the addition of PA6co6T containing linear rigid segments conducts remarkable refinement of spherulites for the blends. Significantly different changes in the crystallographic form, spherulite size, crystalline content and perfection due to the introduction of PA6co6T for the two blends are ascribed to their varied thermomechanical histories and the presence of interchange reaction only for the in‐situ blends. On the basis of the characterizations of the microstructures, the different trends of changes in the mechanical properties with the addition of PA6co6T for the two fabrication methods are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 201–211, 2008     

尼龙6/SiO_2纳米复合材料的制备及其力学性能和热稳定性

以表面含有氨基的可反应性纳米SiO2(RNS-A)和表面含有烷基碳链的可分散性纳米SiO2(DNS-3)作为填料,利用原位聚合法制备了尼龙6/SiO2纳米复合材料(相应的复合材料分别简记为RPA和DP3);采用透射电子显微镜观察了复合材料中纳米SiO2的表面形貌,并利用热失重分析仪测定了复合材料的热稳定性,进而考察了纳米SiO2表面功能基团对尼龙6力学性能和热稳定性的影响.结果显示,纳米SiO2能够很好地分散在尼龙6基体中,并使尼龙6的热分解温度提高10℃左右.与此同时,RPA的最大拉伸强度和冲击强度较纯尼龙6的分别提高34.5%和12.5%,DP3的最大拉伸强度和冲击强度分别提高18.2%和45.7%.这表明两种纳米SiO2均可以有效地提高尼龙6的力学性能和热稳定性;可以推测,纳米SiO2的增强效应与其在尼龙6基体材料中的分散和界面作用有关.     

Preparation of ZnO nanoparticle‐reinforced polyamide 6 composite by in situ‐coproduced method and their properties

Polyamide 6/ZnO nanocomposites (noted as PA6/ZnO) were prepared by an in situ co‐producing method, during which Zn₂(OH)₂CO₃ decomposed into nano‐ZnO in the process of the opening‐ring polymerization of caprolactam at high temperature. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were used to analyze the size and dispersive properties of nano‐ZnO, the crystallization and melting properties, the thermal properties, and crystal structure of PA6/ZnO composite, respectively. The results showed that the nano‐ZnO derived from Zn₂(OH)₂CO₃ via in situ polymerization of PA6‐ZnO was uniformly dispersed in PA6 matrix. However, the overall nano‐ZnO crystallization rate and crystal size in the PA6 matrix were hindered by the bulky PA6 molecular chains. The mechanical properties were evaluated using universal tensile and impact testing instruments. The results revealed that PA6/ZnO composite with 0.2% nano‐ZnO content possessed excellent tensile strength, enhanced by 75% in comparison with the pure PA6. The nano‐ZnO had little influence on the impact strength of PA6. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 165–170     

Thermal properties of polyamide 6/polyurethane blends

Equilibrium melting temperatures and crystallization parameters of polyamide 6/polyurethane blends were investigated. Thermal properties of the crystalline phase of blends obtained from polyamide 6 and polyurethane containing 40 wt% of hard segments, are only limited influenced by the overall blend compositon. Because from separate measurements single glass transitions for all samples were estimated, so in the investigated case the blending process may occur mainly between amorphous fraction of polyamide 6 and the polyurethane or, what is more probable, the polyurethane phase is dispersed in the continuous polyamide matrix, although some interactions exist.     

Preparation and nonisothermal crystallization behavior of polyamide 6/montmorillonite nanocomposites

Polyamide 6 (PA6)/montmorillonite (MMT) nanocomposites were prepared via melt intercalation. The structure, mechanical properties, and nonisothermal crystallization kinetics of PA6/MMT nanocomposites were investigated by X‐ray diffraction (XRD), tensile and impact tests, and differential scanning calorimetry (DSC). Before melt compounding, MMT was treated with an organic surfactant agent. XRD traces showed that PA6 crystallizes exclusively in γ‐crystalline structure within the nanocomposites. Tensile measurements showed that the MMT additions are beneficial in improving the strength and the stiffness of PA6, at the expense of tensile ductility. Impact tests revealed that the impact strength of PA6/MMT nanocomposites tended to decrease with increasing MMT content. The nonisothermal crystallization DSC data were analyzed by Avrami, Ozawa, modified Avrami‐Ozawa, and Nedkov methods. The validity of these empirical equations on the nonisothermal crystallization process of PA6/MMT nanocomposites is discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2878–2891, 2004     

Morphology and mechanical properties of a novel amorphous polyamide/nanoclay nanocomposite

A novel amorphous polyamide/montmorillonite nanocomposite based on poly(hexamethylene isophthalamide) was successfully prepared by melt intercalation. Wide angle X-ray diffraction and transmission electron microscopy showed that organoclay containing quaternary amine surfactants with phenyl and hydroxyl groups was delaminated in the polymer matrix resulting in well-exfoliated morphologies even at high montmorillonite content. Differential scanning calorimetry results indicated that clay platelets did not induce the formation of a crystalline phase in this amorphous polymer. Tensile tests demonstrated that the addition of nanoclay caused a dramatic increase in Young's modulus (almost twofold) and yield strength of the nanocomposites compared with the homopolymer. The nanocomposites exhibited ductile behavior up to 5 wt % of nanoclay. The improvement in Young's modulus is comparable with semicrystalline aliphatic nylon 6 nanocomposites. Both the main chain amide groups and the amorphous nature of the polyamide are responsible for enhancing the dispersion of the nanofillers, thereby, leading to improved properties of the nanocomposites. The structure-property relationship for these nanocomposites was also explored. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2605–2617, 2008     

Films on amorphous polyamide nanocomposites: structure and properties

The ability of a nanoclay to improve the transport and mechanical properties of amorphous polyamide (aPA)‐based films was studied as a function of the draw ratio (DR) and the nanoclay content. The presence of nanoclay did not hinder the drawing ability as the maximum DR of the nanocomposites (NCs) and of the aPA were almost the same (51 for the aPA and from 51 to 55 for the NCs). The high degree of exfoliation and orientation along the drawing direction led to a 30% reduction in the water diffusion coefficient compared with the aPA. Moreover, the already low permeability of the aPA to oxygen was halved. The modulus of elasticity presented unusual increases both in the machine and transverse directions. Both increases of properties were attributed to the planar geometry of the oriented nanoclay sheets. The effects of the presence of nanoclay on the modulus of elasticity in the draw direction in addition to the effects caused by drawing lead to a combined modulus increase of 65% in the highly drawn 6%NC films. The nanoclay also reduced the modulus anisotropy of the films. An increase in either the nanoclay content or the DR causes a decrease in ductility due to both the stress concentrations created by the nanoclay and to the increasing number of chain segments located parallel to the drawing direction. The dimensional stability of the films greatly increased as the addition of 6% nanoclay led to a 70% decrease in creep deformation after 120 h. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of maleic anhydride-grafted ethylene-propylene rubber on the mechanical, rheological and morphological properties of organoclay reinforced polyamide 6/polypropylene nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic modified montmorillonite (organoclay) were compatibilized with maleic anhydride-grafted ethylene-propylene rubber (EPRgMA). The blends were melt compounded in twin screw extruder followed by injection molding. The mechanical properties of PA6/PP nanocomposites were studied by tensile and flexural tests. The microstructure of the nanocomposite were assessed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The dynamic mechanical properties of the PA6/PP blend-based nanocomposites were analyzed by using a dynamic mechanical thermal analyzer (DMTA). The rheological properties were conducted from plate/plate rheometry via dynamic frequency sweep scans. The melt viscosity in a high shear rate region was performed by using a capillary rheometer. The strength and stiffness of the PA6/PP-based nanocomposites were improved significantly with the incorporation of EPRgMA. Adding EPRgMA to the PA6/PP blends resulted in a finer dispersion of the PP phase. TEM and XRD results revealed that the organoclay was dispersed more homogeneously in the presence of EPRgMA, however, mostly in the PA6 phase of the blends. DMTA results showed that EPRgMA worked as an effective compatibilizer. The storage (G′) and loss moduli (G″) assessed by plate/plate rheometry of PA6/PP blends increased with the incorporation of EPRgMA and organoclay. Furthermore, the apparent shear viscosity of the PA6/PP blend increased significantly for the EPRgMA compatibilized PA6/PP/organoclay nanocomposite. This was traced to the formation of an interphase between PA6 and PP (via PA6-g-EPR) and effective intercalation/exfoliation of the organoclay.     

Novel phosphate glass/polyamide 6 hybrids: Miscibility,crystallization kinetics,and mechanical properties

The miscibility, crystallization kinetics, and mechanical properties of a novel low T_g phosphate glass (Pglass)/polyamide 6 hybrid material were investigated. Here, we report the first evidence for miscibility of inorganic phosphate glass and organic polymer prepared by blending both components in the liquid phase using conventional polymer processing methods. From classical melting point depression measurements, we obtained a chi interaction parameter (χ) of −0.067 for the Pglass/polyamide 6 hybrid, indicating that the inorganic glass and polyamide 6 are miscible. The crystallization kinetic parameters for the hybrids were determined using the Avrami approach and found to depend on the volume fraction of Pglass present in the system. In addition, we studied both the dynamic and static mechanical behavior of the hybrids. The results showed a single T_g that decreased by up to 10 °C with increasing phosphate glass volume percent for the hybrids, giving further evidence for the hybrid component miscibility and plasticizing action of the phosphate glass in the pure polyamide 6, respectively. The tensile (static) mechanical properties of the hybrids were found to be remarkably similar to those obtained from typical polymers plasticized with relatively low molecular weight compounds. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 441–450, 2006     

Molecular dynamics and mechanical properties correlations of PA6/PPO blends compatibilized with SMA

The effects of the compatibilizer, styrene maleic anhydride (SMA‐8% MA) upon the change of morphology and molecular dynamics of polyamide‐6 (PA6) and poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) blends were investigated by means of solid‐state NMR techniques. With increasing amounts of SMA, the domains correspond to PA6 and PPO are reduced and the polymer segmental mobility increased. The correlation between NMR relaxation time, T, and the bulk mechanical properties provide a molecular level understanding of the modification of molecular dynamics by the compatibilizer (SMA). The correlation shows that the tensile strength is governed mainly by the morphology, but modulated by the PA6 crystallinity, while the tensile elongation and impact strength are closely affected by both the molecular mobility and morphology. The annealing process improved only the tensile strength, but deteriorated tensile elongation and impact strength due to the increase of PA6 crystallinity, which induced phase separation after annealing. This study raised an important point that the polymer mechanical properties are most sensitive to the molecular structure and dynamics take place within the range of 20 Å to few hundred Å. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1155–1163, 1999     

DSC Studies on Melting and Crystallization of Polyamide 6/Biopol Blends

Blends obtained from Biopol D600G and polyamide 6 reveal in DSC investigations multiphase structure with a distinct crystalline polyamide 6 phase. Due to rapid crystallization of the polyamide 6 the crystallization of the Biopol D600G is retarded. The grade of crystallization of Biopol D600G is lower in the blends than in the pure state, as calculated from the melting enthalpies. Crystallization of polyamide 6 in the blends is faster and results in increasing of the grade of crystallization of polyamide 6 phase comparing to the unblended component. This revised version was published online in August 2006 with corrections to the Cover Date.     

加工条件对聚丙烯/尼龙6原位成纤复合材料的影响

分别用不同的加工温度、挤出螺杆转速、牵引速率在单螺杆挤出机中挤出PP／N6（聚丙烯／尼龙6）共混物，得到不同加工条件下的PP／N6原位成纤复合材料．对不同加工条件下得到的共混物的分散相形态、力学性能进行研究．发现螺杆转速越高、牵引速率越快、加工温度越低，分散的N6纤维尺寸越小，复合材料的力学性能越好．     

The effect of electrophoretic deposition p-aminobenzenesulfonamide grafted CNT on mechanical properties of carbon fiber filled polyamide 6 composite

The surface treatment of carbon fiber is carried out by electrophoretic deposition of p-aminobenzenesulfonamide grafted carbon nanotube (CNT), and it is used as a reinforcement of polyamide 6. The monofilament tensile test and XPS were used to study the effect of p-aminobenzenesulfonamide concentration on the tensile strength and surface functional groups of carbon fiber monofilaments. The results show that the higher the p-aminobenzenesulfonamide concentration, the greater the decrease in the mechanical properties of carbon fibers, and the greater the content of oxygen-containing functional groups on the surface. It is preferred that carbon fiber and thermoplastic polyamide 6 with higher retention rate of monofilament tensile strength and rich oxygen-containing functional group content are made into composite materials, and the interlaminar shear strength (ILSS) is evaluated.     

Effects of reprocessing on the structure and properties of polyamide 6 nanocomposites

PA6 based nanocomposites (NCs) were reprocessed by repeated injection moulding to find out whether reprocessing is possible in these materials by means of the observation of the changes in the structure and mechanical properties. The studied variables were (a) the number of cycles (1-5), (b) the origin of the NC: either laboratory mixed or commercial and (c) the processing temperature (230 °C and 270 °C). Neat PA6 was also reprocessed as a reference material. In spite of the colour change, the Young's modulus, the solid state characteristics and the dispersion level were preserved upon reprocessing. The lack of change of chemical nature observed by FTIR, and the observed decreases in viscosity indicated that the main effect of reprocessing was a decrease in the molecular weight. At 230 °C the decreases in viscosity were smaller after reprocessing, and almost no change was seen in the structural parameters and properties. The decrease in the molecular weight after reprocessing at 270 °C leads to lower ductility and mainly to a decrease in the ability of the nPA6 matrix to cold draw. However, no change of the interphase conditions or agglomeration of the OMMT was detected and the NCs remained clearly ductile; thus, revealing a lack of deterioration of the interface and the ability of the NCs for recycling.     

The effect of MWCNT on dynamic mechanical properties and crystallinity of in situ polymerized polyamide 12 nanocomposite

This work aims at investigating the dynamic mechanical properties of in situ anionic ring opening polymerized polyamide 12 in the presence of multi‐walled carbon nanotubes (MWCNT). According to the dynamic mechanical thermal analysis results, the addition of only 0.1 wt.% of MWCNTs led to 30% enhancement in modulus at room temperature which exhibited improved mechanical behavior of the nanocomposites. Test results showed that by the presence of 1.2% wt MWCNTs, the modulus is almost doubled, and it did not show any tangible changes by the addition of more nanotubes. Also, the effect of different frequencies on the viscoelastic behavior was investigated in order to determine the thermal transitions occurred in the synthesized nanocomposites. After that, the crystallinity of the samples has been studied using differential scanning calorimetry and X‐ray diffraction data in order to investigate the effect of MWCNT content on the crystals' dimension.     

Physical and mechanical properties of graphene oxide/polyethersulfone nanocomposites

The aim of this study was to investigate physical and mechanical properties of graphene oxide (GO)/polyethersulfone (PES) nanocomposite films. The films were produced by solution casting method. The mechanical properties of composite films were evaluated by tensile test. A significant enhancement in the mechanical properties of neat PES films was obtained incorporating a small amount of GO loading (0.05–1 wt.%). The highest tensile strength was observed at 1 wt.% of GO. Comparisons were made between experimental data and the Halpin–Tsai model predictions for the tensile strength and modulus of GO/PES composites. The effect of an orientation factor on model predictions was also acquired. The hydrophilicity of the nanocomposite was evaluated by assessing contact angle and enhanced wet ability of the films was obtained with increasing the amount of GO up to 1%. The morphology of the nanocomposites was investigated using scanning electron microscopy and transmission electron microscopy and the results revealed a good dispersion of GO in the PES matrix. The thermal behavior of the composite was also studied. Thermal stability of composites was increased by adding the GO. Copyright © 2013 John Wiley & Sons, Ltd.     

Non-isothermal crystallization behaviors of polyamide 6/clay nanocomposites

The non-isothermal crystallization behaviors of polyamide 6/clay nanocomposite (PA6CN) were investigated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). DSC results showed that the nanometric silicate layers in PA6CN acted as effective nucleation agents. The addition of silicate layers influenced the mechanism of nucleation and the growth of PA6 crystallites. The DSC results also implied an unusual phenomenon, in contrast to PA6, the crystallinity degree of PA6CN increased with increasing cooling rate. XRD results verified this phenomenon and indicated that the addition of silicate layers favored the formation of the γ crystalline form.