Comparison of the toughening behavior of nylon 6 versus an amorphous polyamide using various maleated elastomers

The toughening effect of two types of elastomers based on ethylene/α-olefin copolymers, viz, an ethylene/propylene copolymer (EPR) with its maleated version, EPR-g-MA, and an ethylene/1-octene copolymer (EOR) with its maleated versions, EOR-g-MA-X% (X=0.35, 1.6, 2.5), for two classes of polyamides: semi-crystalline nylon 6 versus an amorphous polyamide (Zytel 330 from DuPont), designated as a-PA, was explored. The results are compared with those reported earlier based on a styrenic triblock copolymer having a hydrogenated midblock, SEBS, and its maleated version, SEBS-g-MA, elastomer system. Izod impact strength was examined as a function of rubber content, rubber particle size and temperature. All three factors influence the impact behavior considerably for the two polyamide matrices. The a-PA is found to require a somewhat lower content of rubber for toughening than nylon 6. Very similar optimum ranges of rubber particle sizes were observed for ternary blends of EOR-g-MA/EOR with each of the two polyamides while blends based on mixtures of EPR-g-MA/EPR and SEBS-g-MA/SEBS (where the total rubber content is 20% by weight) show only an upper limit for a-PA but an optimum range of particle sizes for nylon 6 for effective toughening. Higher EPR-g-MA contents lead to lower ductile-brittle transition temperatures (T_db) as expected; however, a-PA binary blends with EPR-g-MA have a much lower T_db than do nylon 6 blends when the content of the maleated elastomer is not high. A minimum in plots of ductile-brittle transition temperature versus particle size appears for ternary blends of each of the matrices with EOR-g-MA/EOR; blends based on SEBS-g-MA/SEBS, in most cases, show higher ductile-brittle transition temperatures, regardless of the matrix. However, blends with EPR-g-MA/EPR show comparable T_db with those based on EOR-g-MA/EOR for the amorphous polyamide but show the lowest ductile-brittle transition temperatures for nylon 6 within the range of particle sizes examined. For the blends with a bimodal size distribution, the global weight average rubber particle size is inappropriate for correlating the Izod impact strength and ductile-brittle transition temperature. In general, trends for this amorphous polyamide are rather similar to those of semi-crystalline nylon 6.     

Effect of organoclay structure on morphology and properties of nanocomposites based on an amorphous polyamide

An amorphous polyamide (a-PA) and three organoclays, M₃(HT)₁, M₂(HT)₂ and (HE)₂M₁T₁, were melt processed to explore the effect of the organoclay structure on the extent of exfoliation and properties of these nanocomposites. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to determine the degree of exfoliation of the nanocomposites. For quantitative assessment of the structure of the nanocomposites, a detailed particle analysis was made to provide various averages of the clay dimensions and aspect ratio. The results evaluated from different methods were generally consistent with each other. Nanocomposites based on the organoclays with one alkyl tail and hydroxyl ethyl groups gave well-exfoliated structures and high matrix reinforcement while nanocomposites from two-tailed organoclay contain a considerable concentration of intercalated stacks. Nanocomposites from the organoclays with one alkyl tail showed slightly better exfoliation and matrix reinforcement than those from the organoclays with hydroxyl ethyl groups. The organoclay structure trends for a-PA are analogous to what has been observed for nylon 6; this suggests that a-PA, like nylon 6, has good affinity for the pristine silicate surface of the clay leading to better exfoliation and enhanced mechanical properties with one-tailed organoclay than multiple-tailed organoclay. Furthermore, heat distortion temperatures were predicted from the dynamic mechanical properties of nanocomposites.     

Effect of organoclay structure and mixing protocol on the toughening of amorphous polyamide/elastomer blends

An amorphous polyamide (a-PA) was blended with an ethylene-1-octene (EOR) elastomer with organoclays present to control the elastomer particle size. Four different organoclays, M₃(HT)₁, M₂(HT)₂, M₁H₁(HT)₂, and (HE)₂M₁T₁ and two different mixing protocols were used to investigate the effect of the organoclay structure and mixing protocol on the morphology and properties of the resulting blends. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to evaluate the degree of exfoliation of the organoclays and the morphology of the elastomer particles for these blends. A detailed particle analysis was made to provide a quantitative assessment of elastomer particle size. The size and shape of the elastomer particles were dramatically affected by the amount of organoclay but the organoclay type and the mixing protocol led to slight differences. Broadly speaking, most of the MMT platelets are well exfoliated in the a-PA phase, but some locate at the interface and tend to envelop the EOR phase. The mechanical properties were not significantly affected by the organoclay type or the mixing protocol. While the organoclays reduced the EOR particles to size range where toughness might be expected, all blends proved to be brittle. A clear trade-off was observed between the Izod impact strength and tensile modulus for these blends containing organoclays.     

Comparison of fracture behavior of nylon 6 versus an amorphous polyamide toughened with maleated poly(ethylene-1-octene) elastomers

The fracture behavior of an amorphous polyamide (Zytel 330 from DuPont), a-PA, and nylon 6 toughened by maleated poly(ethylene-1-octene) elastomers are reported. The deformation mechanisms during fracture were verified by examining an arrested crack tip and the surrounding regions using transmission electron microscopy analysis. a-PA blends show higher levels of impact strength and lower ductile-brittle transition temperatures than nylon 6 blends. Fracture toughness, characterized by both linear elastic fracture mechanics techniques in terms of the critical strain energy release rate, G_IC, and the essential work of fracture methodology, i.e. the limiting specific fracture energy, u_o, and the dissipative energy density, u_d, using thick (6.35 mm) samples with sharp notches, depends on ligament length, rubber content, rubber particle size and test temperature. In general, a-PA blends show larger values of u_d than do nylon 6 blends while the opposite is seen for u_o. The amorphous polyamide shows a similar critical upper limit on rubber particle size, or interparticle distance, for toughening as the semi-crystalline nylon 6; thus, it is clear that the crystal morphology around the rubber particles must not be the dominant cause of this critical size scale. The deformation mechanisms involved include cavitation of rubber particles followed by some crazing and then massive shear yielding of the matrix.     

Mechanical characterization of toughened polyamide‐6 blends with metallocene copolymers

The effectiveness as impact modifier of two in situ maleated metallocene copolymers, a metallocene polyethylene, (mPE1) and a metallocene ethylene‐propylene (mEPDM) and three commercial maleated copolymers (mPE2‐g‐MA, EPDM‐g‐MA, and mEPR‐g‐MA) were studied in binary and ternary blends carried out in an intermeshing corotating twin‐screw extruder with polyamide‐6 (PA) as matrix (80 wt %). Also, the effects of the grafting degree, viscosity ratio, and crystallinity of the dispersed phases on the morphological and mechanical properties of the blends were investigated. A significant improvement of the compatibility of these grafted copolymers with PA6 was shown by FTIR spectroscopy, capillary rheometry, and scanning electron microscopy (SEM) in all reactive blends. The tensile strength values of the mEPR‐g‐MA/PA2 binary blend showed the highest strain hardening. The results obtained in this work indicated that the effectiveness of the grafted copolymers as impact modifier depends on the morphology of the blends and a combination of tensile properties of the blend components such as Young's modulus, Poisson ratio, and break stress. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comparative performance of carbon nanotube and nanoclay on thermal properties and flammability behavior of amorphous polyamide/SEBS blend

Multiwall carbon nanotubes (CNT) or montmorillonite clay (MMT-30B) were added to a poly(hexamethylene isophthalamide-co-terephthalamine) (an amorphous polyamide - aPA) and styrene-ethylene/butylene-styrene graphitized with maleic anhydride (SEBS) blend, in different concentrations, in order to investigate the morphology, thermal properties and flammability behavior. Different nanoparticle localizations in the phase blend were observed through transmission electronic microscopy. CNT nanoparticles are localized in SEBS phase, and MMT-30B nanoparticles in aPA phase. No significant changes were observed on transition temperatures and thermal stability with both nanoparticle additions. However, a slight increase on storage modulus for clay nanocomposites and a slight reduction for carbon nanotube nanocomposites were observed, due to their different phase localizations. Regarding flammability, CNT nanocomposites showed better performance as a flame retardant when compared to samples with MMT-30B. Although the MMT-30B nanocomposites could not be classified according to the UL-94 criteria, no dripped flaming particles were observed, due to the a char barrier formation on the polymer surface. The CNT nanocomposites were classified according to the UL-94 criteria as V-2. The CNT's selective localization on the SEBS phase decreases its heat-release rate, but no interconnected network structure was formed in the matrix to suppress the dripping flaming particles.     

Effects of addition of acrylic compatibilizer on the morphology and mechanical behavior of amorphous polyamide/SAN blends

Amorphous polyamide (aPA)/acrylonitrile‐styrene copolymer (SAN) blends were prepared using methyl methacrylate‐maleic anhydride copolymer MMA‐MA as compatibilizer. The aPA/SAN blends can be considered as a less complex version of the aPA/ABS (acrylonitrilebutadiene‐styrene) blends, due to the absence of the ABS rubber phase in the SAN material. It is known that acrylic copolymer might be miscible with SAN, whereas the maleic anhydride groups from MMA‐MA can react in situ with the amine end groups of aPA during melt blending. As a result, it is possible the in situ formation of aPA‐g‐MMA‐MA grafted copolymers at the aPA/SAN interface during the melt processing of the blends. In this study, the MA content in the MMA‐MA copolymer and its molecular weight was varied independently and their effects on the blend morphology and stress–strain behavior were evaluated. The morphology of the blends aPA/SAN showed a minimum in the SAN particle size at low amounts of MA in the compatibilizer, however, as the MA content in the MMA‐MA copolymer was increased larger SAN particle sizes were observed in the systems. In addition, higher MA content in the compatibilizer lead to less ductile aPA/SAN blends under tensile testing. The results shown the viscosity ratio also plays a very important role in the morphology formation and consequently on the properties of the aPA/SAN blends studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and thermal oxidative degradation 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 surfactant with phenyl groups was delaminated in the polymer matrix, resulting in well-dispersed morphologies even at high montmorillonite content. Thermal oxidation behavior of the polymer nanocomposites was studied by thermogravimetric analysis (TGA), and the chemical evolution in the solid residue was monitored by elemental analysis and Fourier transform infrared spectroscopy (FTIR). TGA results showed that the addition of well-dispersed organoclay resulted in a substantial increase (30 °C) in the onset degradation temperature of the nanocomposites as compared to the homopolymer. Elemental analysis on the solid residue indicated that the presence of nanoclay resulted in char formation with greater thermal stability. FTIR spectra showed that thermal degradation in air occurred via both oxidative and non-oxidative mechanisms simultaneously. In the homopolymer, the oxidative mechanism was more dominant. However, with the addition of well-dispersed organoclay, the non-oxidative pathway became more significant. Hence the presence of delaminated nanoclay layers could effectively retard thermo-oxidative degradation of the amorphous polymer by constraining the polymer chains and slowing down the rate of oxygen diffusion through the nanocomposites, but it was not as effective in hindering the non-oxidative degradation reaction pathway.     

EPDM/St‐An graft copolymerization reaction behavior by phase inversion emulsion and the toughness effect of EPDM‐g‐SAN on SAN resin

Styrene‐EPDM‐acrylonitrile tripolymer (EPDM‐g‐SAN) was synthesized by the graft copolymerization of styrene (St) and acrylonitrile (An) onto ethylene‐propylene‐diene terpolymer (EPDM) with “phase inversion” emulsification technique. The high impact strength engineering plastics AES was the blend of SAN resin and EPDM‐g‐SAN, which occupied good weathering and yellow discoloration resistivity. The effects of An percentage in comonomer and the weight proportion of EPDM to St‐An on graft copolymerization behavior and AES notched impact strength were studied. The results showed that monomer conversion ratio (CR) exhibited a peak when the An percentage changed, and the maximum value was 97.5%. Grafting ratio (GR) and grafting efficiency (GE) enhance as well. The notched impact strength of AES presented a peak with the maximum value of 53.0 KJ/m², when An percentage was at the range of 35–40%. The spectra of FTIR showed that St and An were graft onto the EPDM. DSC analysis illuminated that T_g of EPDM phase in the blends was lower than that of the pure EPDM. TEM and SEM micrographs indicated that the polarity of g‐SAN of EPDM‐g‐SAN was the main factor effect the particle morphology, in terms of size, distribution and isotropy. When weight ratio of St to An was 65/35, the polarity of g‐SAN chains was appropriate, and the EPDM‐g‐SAN particles dispersed well in the SAN matrix. The super impact toughness is interpreted in terms of EPDM phase cavitation and enhanced plastic shear yielding. The highest toughness occurs at an optimum EPDM‐g‐SAN phase particle size which is about 0.2 μm in SAN resin matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Unexpected partial crystallization of an amorphous polyamide as induced by combined temperature and humidity

In this study, it is presented for the first time, the characterization of an amorphous polyamide after having been subjected to humid thermal conditions such as those typically applied in the industrial sterilization of packaged foods. From a fundamental point of view, it was fortuitously found that the combination of heat and moisture, with and without the assistance of pressure, was capable of inducing some crystallization in the otherwise amorphous polymer. Characterization of the crystallization process was carried out by differential scanning calorimetry, Fourier transform infrared, and simultaneous time‐resolved small and wide angle X‐ray scattering synchrotron experiments. The crystallization of the polymer began as characterized by wide angle X‐ray scattering and differential scanning calorimetry in the presence of humidity at ～90°C and extended up to 120°C under autoclave conditions, and it is thought to be the result of heated moisture being able to disrupt the intense amide groups self‐association. Thus, the thermally activated molecular structure is thought to become plasticized by the combined presence of heat and water which, in turn, provoke sufficient segmental molecular mobility in the system to promote some degree of lateral order. Propertywise, the resulting consequences of this behavior are an increase in the barrier properties to oxygen and a reduction in water sorption. From an applied view point, it is suggested that this unexpected behavior could make this polymer of significant interest in retortable food packaging applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1216–1223, 2006     

Compatibilization of polyethylene/polyamide 6 blends with oxazoline‐functionalized polyethylene and styrene ethylene/butylene styrene copolymer (SEBS)

Study was made of the compatibilization of polyethylene/polyamide 6 (PE/PA6) blends with a ricinoloxazoline maleinate grafted polyethylene and styrene ethylene/butylene styrene copolymer. The blends were prepared in a twin‐screw midiextruder, and the specimens for mechanical tests were injection molded with a mini‐injection molding machine. The effect of compatibilizing on the mechanical properties and the morphology of the blends was studied. The toughness and ductility of the blends were substantially improved as a result of the compatibilization. Simultaneously, the strength and stiffness were slightly reduced. Morphological studies showed that the particle size was reduced and the adhesion of the dispersed phase to the matrix was improved by the compatibilization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1443–1450, 1999     

Rubber toughened polyamide 6: The influences of compatibilizer on morphology and impact properties

In this study, styrene-(ethylene-co-butylene)-styrene (SEBS) triblock copolymer (Kraton G-1652) was modified with maleic anhydride (MA). The maleated SEBS was used as compatibilizer for the blends of Nylon 6 (PA6) and SEBS. The morphology and impact strength of the blends were measured as functions of concentration and MA graft ratio of maleated SEBS. The compatibility and fracture mechanism of the blends were evaluated from the SEM micrographs of the xylene-etched surfaces and of fractured surfaces. Some of the blends exhibited an impact strength up to about 30 fold greater than neat PA6. The fracture involved both both cavitation and shear yielding. The mechanism of compatibilization of maleated SEBS in the ternary components blends was proposed.     

Mechanical properties and morphology of PA6/EVA blends

The mechanical properties of blends of polyamide6 (PA6) and ethylene vinyl acetate (EVA) at a blending composition of 0–50 wt % EVA were studied. The notched Izod impact strength of PA6 increased with the incorporation of EVA, the increase being more than 100% compared to PA6 at 10% EVA. The tensile strength and the tensile modulus of the blends decreased steadily as the weight percent of EVA increased. Analysis of the tensile data using predictive theories indicated the extent of the interaction of the dispersed phase and the matrix up to 20 wt % EVA. SEM studies of the cryogenically fractured surfaces indicated increase in the dispersed phase domain size with EVA concentrations. On the other hand, impact fractured surfaces of PA6/EVA blends indicated debonding of EVA particles, leaving hemispherical bumps, indicating inadequate interfacial adhesion between PA6 and EVA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1593–1606, 2002     

EPDM-g-MAH增韧PA 6

制备了三种不同黏度的马来酸酐接枝三元乙丙橡胶(EPDM-g-MAH),将其用于增韧聚酰胺(PA)6。通过傅里叶变换红外光谱、扫描电子显微镜、差示扫描量热法、力学性能测试等表征了三元乙丙橡胶(EPDM)对增韧PA 6体系结构与性能的影响。结果表明:EPDM-g-MAH改善了PA 6与EPDM的相容性,用黏度适中的EPDM得到的EPDM-g-MAH与PA 6(质量比为85∶15)共混,分散相尺寸较小且分散均匀,共混体系的力学性能得到提高,特别是Izod缺口冲击强度几乎为PA 6的10倍。     

Elastomer particle morphology in ternary blends of maleated and non-maleated ethylene-based elastomers with polyamides: Role of elastomer phase miscibility

The elastomer particle morphology in ternary blends of maleated and non-maleated ethylene-based elastomers with polyamides has been examined. The elastomers used include an ethylene/propylene copolymer, EPR, with a maleic anhydride (MA) grafted version, EPR-g-MA, and an ethylene/1-octene copolymer, EOR, with maleated versions EOR-g-MA-X% where X is 0.35, 1.6 or 2.5. The polyamides used were nylon 6 and an amorphous polyamide, Zytel 330 from DuPont. The morphology development was explored from both thermodynamic and kinetic points of view where the former refers to miscibility of the elastomers and the latter might include the ratio of the elastomers, the matrix type, the order of mixing, mixing intensity, i.e. the extruder type, and graft structure, etc. Both sources influence the morphology developed. For ternary blends with EPR-g-MA/EPR, the morphology (particle size and distribution) seems to be well controlled via the level of maleation in the rubber phase. The two polyamides generate comparable rubber particle sizes at the same of MA level. For ternary blends with EOR-g-MA/EOR, the morphology strongly depends on the level of MA; the rubber particle size, in general, is much smaller in nylon 6 blends than in Zytel 330 blends. Morphology of ternary blends with EOR-g-MA/EOR is much more complex than that of blends with EPR-g-MA/EPR due to the co-existence of miscibility limits and the kinetic factors. Miscibility of maleated EOR elastomers is examined via transmission electron microscopy (TEM) using a special staining technique; a miscibility boundary, as revealed by TEM, occurs around Δ(%MA)=0.9−1.25 MA%. If the two elastomers are miscible, a unimodal particle size distribution always appears in blends regardless of the kinetic factors; however, if immiscibility prevails, either a unimodal or bimodal particle size distribution may develop depending on the ratio of the elastomers and the matrix type. The order of mixing and the mixing intensity do not seem to change the modality of the size distribution.     

Blends of polyamide1010 with unmodified and maleic‐anhydride‐grafted high‐impact polystyrene

The crystallization behaviors, dynamic mechanical properties, tensile, and morphology features of polyamide1010 (PA1010) blends with the high‐impact polystyrene (HIPS) were examined at a wide composition range. Both unmodified and maleic‐anhydride‐(MA)‐grafted HIPS (HIPS‐g‐MA) were used. It was found that the domain size of HIPS‐g‐MA was much smaller than that of HIPS at the same compositions in the blends. The mechanical performances of PA1010–HIPS‐g‐MA blends were enhanced much more than that of PA1010–HIPS blends. The crystallization temperature of PA1010 shifted towards higher temperature as HIPS‐g‐MA increased from 20 to 50% in the blends. For the blends with a dispersed PA phase (≤35 wt %), the T_c of PA1010 shifted towards lower temperature, from 178 to 83°C. An additional transition was detected at a temperature located between the T_g's of PA1010 and PS. It was associated with the interphase relaxation peak. Its intensity increased with increasing content of PA1010, and the maximum occurred at the composition of PA1010–HIPS‐g‐MA 80/20. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 857–865, 1999     

Compatibilizing effect of a maleic anhydride functionalized SEBS triblock elastomer through a reaction induced phase formation in the blends of polyamide6 and polycarbonate—III. Microscopic studies on the deformation mechanism

Microscopic studies on the deformation mechanism of the blends of polyamide6 (PA6) and polycarbonate (PC) compatibilized with triblock copolymer of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) functionalized with maleic anhydride (SEBSgMA) were carried out. As described in our previous paper, significant improvement of mechanical properties of this blend series can be achieved by the use of the combination of SEBSgMA and unmodified SEBS (unSEBS) as compatibilizers. Especially, when the composition of the blends of PA6/PC is and the total amount of added SEBS is 20 phr, drastic enhancement of the impact strength and of the elongation at break in the tensile stress-strain tests can be achieved by varying the ratio of SEBSgMA to unSEBS. The encapsulation by SEBS on the PC domains gradually become incomplete as the increase of the ratio of unSEBS to SEBSgMA and then the mechanical properties can be maximized. We observed the deformed zone of the specimens loaded to the tensile stress-strain tests and to the Izod impact tests using transmission electron microscopy (TEM) in order to find out the origin of this enhancement of the mechanical properties. It has revealed that voids tend to be generated at the PA6/PC interface easily due to the incompletion of the encapsulation achieved by the use of the combination of SEBSgMA and unSEBS, and thereby the local shear yielding of the matrix is promoted to dissipate the tensile and the impact energy. © 1997 Elsevier Science Ltd.     

Deformation and fracture behavior of polyamide nanocomposites: The effect of clay dispersion

This study describes the effect of the clay content and its dispersion on deformation and fracture behavior of polyamide nanocomposites. Two nanocomposite systems, intercalated and exfoliated nanocomposites containing layered silicate, were compared. They were prepared by melt‐compounding of polyamide with sodium montmorillonite or organophilized montmorillonite. It has been shown that while the exfoliated structure imparts to the nanocomposite higher stiffness and strength, the toughness is inferior to the intercalated nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(methyl methacrylate‐co‐maleic anhydride) copolymers and its potential as a compatibilizer for amorphous polyamide blends

Poly(methyl methacrylate‐co‐maleic anhydride) copolymers (MMA‐MA) have been synthesized by solution method, using toluene as solvent and benzoyl peroxide as initiator. The MMA‐MA copolymers were characterized by size exclusion chromatography, Fourier transforms infrared spectroscopy (FTIR), and titration. It was found that the modified polymerization procedure used in this work was more effective in controlling the molecular weight when adding different amounts of maleic anhydride (MA) than procedures previously used. In spite of the significant difference in reactivity ratios between MMA and MA, up to 50% of the MA added to the reactor was incorporated into the copolymer. The evidences for reactions of the MA groups of the MMA‐MA copolymer with the amine end groups of the amorphous polyamide (aPA) during melt blending was obtained by rheological measurements. In this work, the molecular weight and the content of MA reactive functional groups in the MMA‐MA copolymer were varied independently and its effects on the interaction with aPA were studied. It was observed that a compromise between molecular weight and the level of reactive functional group of the compatibilizer should be sought to improve the compatibilization of the polymer systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007