Blends of polyamide 6, polycarbonate,and poly(propylene oxide). I. Reactive compatibilization–morphology relationships

The relationship between reactive compatibilization and morphology of the polyamide 6–polycarbonate (PA6–PC) and polyamide 6–polycarbonate–poly(pro-pylene oxide) (PA6–PC–PPO) blends were investigated by means of torque values, scanning electron microscopy, and Fourier transform infrared spectroscopy. The micrographs show that the blends processed for a long period of time presented a PC domain of smaller size and better adherence between the phases than the blends processed for a short period of time. This fact can be related with the presence of the block copolymer of PA6–PC synthesized in situ by the reaction of PA6 and PC and depend on temperature and mixing time. The presence of PPO does not impede the formation of copolymer but interferes on the size of the domain. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 857–864, 1998     

HDPE-g-GMA反应性增容PA66/UHMWPE共混合金性能研究

以甲基丙烯酸缩水甘油酯接枝高密度聚乙烯(HDPE-g-GMA)作为聚酰胺66/超高摩尔质量聚乙烯(PA66/UHMWPE)共混合金的增容剂,采用熔融法制备了PA66/uHMwPE/HDPE-g-GMA共混合金.通过Molau试验、SEM观察和力学性能测试,研究了HDPE-g-GMA在熔融共混过程中对PA66/UHMWPE共混合金的增容作用.结果表明:HDPE-g-GMA与PA66发生了化学反应,所生成的接枝共聚物对PA66/UHMWPE共混合金有较好的增容作用;PA66/UHMWPE共混合金的界面形态和力学性能均有较大改善,吸水率也有所降低.     

Melting behavior and nonisothermal crystallization kinetics of polyamide 6/polyamide 66 molecular composites via in situ polymerization

The melting behavior and nonisothermal crystallization kinetics of pure polyamide 6 (PA 6) and its molecular composites with polyamide 66 (PA 66) were investigated with differential scanning calorimetry. The PA 6/PA 66 composites had one melting peak, whereas the coextruded PA 6/PA 66 blends had two melting peaks. With the addition of PA 66 to PA 6 via in situ anionic polymerization, the melting temperature, crystallization temperature, and crystallinity of PA 6 in the composites decreased. The half‐time of nonisothermal crystallization increased for a PA 6/PA 66 molecular composite containing 12 wt % PA 66, in comparison with that of pure PA 6. The commonly used Ozawa equation was used to fit the nonisothermal crystallization of pure PA 6 and its composites. The Ozawa exponent values in the primary stage were equal to 1.28–3.03 and 1.28–2.97 for PA 6 and its composite with 12 wt % PA 66, respectively, and this revealed that the mechanism of primary crystallization of PA 6 and PA 6/PA 66 was mainly heterogeneous nucleation and growth. All the results indicated that the incorporation of PA 66 into PA 6 at the molecular level retarded the crystallization of PA 6. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2172–2177, 2005     

Co-continuous and encapsulated three phase morphologies in uncompatibilized and reactively compatibilized polyamide 6/polypropylene/polystyrene ternary blends using two reactive precursors

Phase morphology development in ternary uncompatibilized and reactively compatibilized blends based on polyamide 6 (PA6), polypropylene (PP) and polystyrene (PS) has been investigated. Reactive compatibilization of the blends has been performed using two reactive precursors; maleic anhydride grafted polypropylene (PP-g-MA) and styrene maleic anhydride copolymer (SMA) for PA6/PP and PA6/PS pairs, respectively. For comparison purposes, uncompatibilized and reactively compatibilized PA6/PP and PA6/PS binary blends, were first investigated. All the blends were melt-blended using a co-rotating twin-screw extruder. The phase morphology investigated using scanning electron microscope (SEM) and selective solvent extraction tests revealed that PA6/PP/PS blends having a weight percent composition of 70/15/15 is constituted from polyamide 6 matrix in which are dispersed composite droplets of PP core encapsulated by PS phase. Whereas, a co-continuous three-phase morphology was formed in the blends having a composition of 40/30/30. This morphology has been significantly affected by the reactive compatibilization. In the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends, PA6 phase was no more continuous but gets finely dispersed in the PS continuous phase. The DSC measurements confirmed the dispersed character of the PA6 phase. Indeed, in the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends where the PA6 particle size was smaller than 1 μm, the bulk crystallization temperature of PA6 (188 °C) was completely suppressed and a new crystallization peak emerges at a lower temperature of 93 °C as a result of homogeneous nucleation of PA6.     

Improved thermal conductivity of ceramic filler‐filled polyamide composites by using PA6/PA66 1:1 blend as matrix

Polyamide‐type composites with improved thermal conductivity are prepared by using polyamide 6(PA6)/polyamide 6,6 (PA66) 1:1 blend as the matrix and aluminum nitride (AlN) as the filler through melt compounding. Field emission scanning electron microscopy coupled with energy dispersive spectrometry (EDS) mapping of Al is used to investigate distribution of AlN. Differential scanning calorimeter is used to investigate the crystallization behavior of the composites. The thermal conductivity of PA6/PA66/AlN composite with 50 wt % AlN is 1.5 W m^?1 K^?1, 88% enhancement compared to those of single polymer based PA6/AlN or PA66/AlN composites. The reason for the improved thermal conductivity is the increased effective volume concentration of AlN in one (probably PA66) phase. The experimental data are fitted into Bruggeman and Agari–Uno model. Composites with similar thermal conductivity are also prepared using silicon carbide as the filler instead of AlN, showing that using PA6/PA66 1:1 blend as the matrix is a universal method to prepare thermally conductive composites with less filler loading. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45371.     

Study on in situ reinforcing and toughening of a semiflexible thermotropic copolyesteramide in PBT/PA66 blends

Ternary in situ composites based on poly(butylene terephthalate) (PBT), polyamide 66 (PA66), and semixflexible liquid crystalline polymer (LCP) were systematically investigated. The LCP used was an ABA30/PET liquid crystalline copolyesteramide based on 30 mol % of p‐aminobenzoic acid (ABA) and 70 mol % of poly(ethylene terephthalate) (PET). The specimens for thermal and rheological measurements were prepared by batch mixing, while samples for mechanical tests were prepared by injection molding. The results showed that the melting temperatures of the PBT and PA66 phases tend to decrease with increasing LCP addition. They also shifted toward each other due to the compatibilization of the LCP. The torque measurements showed that the ternary blends exhibited an apparent maximum near 2.5–5 wt % LCP. Thereafter, the viscosity of the blends decreased dramatically at higher LCP concentrations. Furthermore, the torque curves versus the PA66 composition showed that the binary PBT/PA66 blends can be classified as negative deviation blends (NDBs). The PBT/PA66/LCP blends containing up to 15 wt % LCP were termed as positive deviation blends (PDBs), while the blends with the LCP ≥25 wt % exhibited an NDB behavior. Finally, the tensile tests showed that the stiffness and tensile strength of ternary in situ composites were generally improved with increasing LCP content. The impact strength of ternary composites initially increased by the LCP addition, then deteriorated when the LCP content was higher than 10 wt %. The correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1975–1988, 2000     

Morphological structure and mechanical properties of In situ microfibrillar composites of modified PA66 with PP

In situ microfibrillar composites (PP/mPA66) of modified polyamide66 (mPA66) with polypropylene (PP) were prepared by using a “post‐compatibilization” technique. The mPA66 was firstly obtained by reactive extrusion of PA66 resin with a specially designed compatibilizer, which was then blended with PP through extrusion combined with a hot stretching and subsequently quenching process. The PP/mPA66 in situ microfibrillar composites were comparatively studied with simply blended samples of PP/PA66 that were prepared by blending PA66 and PP together with (or without) the same compatibilizer through extrusion. PA66‐g‐PP (and/or elastomers) graft copolymer formation in mPA66 was identified by dissolution test and infrared spectroscopy measurement, the compatibilizer is unevenly dispersed with large domains in PA66 as observed by scanning electron microscope (SEM). In PP/mPA66 composites, the in situ generated PA66 microfibrils have a rather nonuniform diameter distribution and a very rough surface. SEM observations for the fractured surface illustrated that PP/mPA66 composites have structural characteristics of stronger adhesion and moderate flexibility of the interface. Enhanced compatibilization between the PA66 microfibrils with the PP matrix resulted in improved mechanical properties of the PP/mPA66 composites. With optimized composition, the PP/mPA66 composite has notched Izod impact strength, flexural modulus, and tensile yield stress of 1.49, 1.16, and 0.99 times as those of the neat PP, respectively. Such enhanced mechanical properties balance and improved interface adhesion were not found in the simply blended samples of PP/PA66 with or without the specially designed compatibilizer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhancing the crystallinity and heat resistance of poly(ethylene terephthalate) using ZnCl2-ionized polyamide-66 as a heterogeneous nucleator

To achieve the maximal improvement in the crystallization rate and heat resistance of poly(ethylene terephthalate) (PET), 2.6 mol% of ZnCl₂ ionized polyamide (PA)-66 (PA-66–Zn), with a strong coordination ability, is prepared and used as PET nucleator. This study found that the PA-66–Zn heterogeneously nucleates PET more effectively than the CaCl₂-ionized PA-66 and non-ionized PA-66 by differential scanning calorimetry, crystallization kinetics, X-ray diffraction, and polarized optical microscopy. This is probably a result of the introduction of stronger ion–dipole interactions (IDIs) between the PET esters and the ionized-PA-66 ZnCl₂-coordinating amides, which obviously heightens the PET/PA-66–Zn interfacial compatibility. As shown by scanning electron microscopy, the compatibilization through an appropriate concentration of IDIs promotes the formation of smaller and denser PA-66 crystals with immensely increased nucleator efficiency. Furthermore, the PET/PA-66–Zn with significantly improved crystallinity displays a remarkable increase in heat-resistant temperature, at 21.6 and 55.1°C higher than that of PET/PA-66 and PET, respectively. The results demonstrate that the PA-66–Zn can act as a superior nucleator and as an outstanding heat-resistant agent for PET.     

Synthesis and properties of reactively compatibilized polyester and polyamide blends

The functionalization of poly(butylene terephthalate) (PBT) has been accomplished in a twin screw extruder by grafting maleic anhydride (MA) using a free radical polymerization technique. The resulting PBT‐g‐MA was successfully used as a compatibilizer for the binary blends of polyester (PBT) and polyamide (PA66). Enhanced mechanical properties were achieved for the blend containing a small amount (as low as 2.5 %) of PBT‐g‐MA compared to the binary blend of unmodified PBT with PA66. Loss and storage moduli for blends containing compatibilizer were higher than those of uncompatibilized blends or their respective polymers. The grafting and compatibilization reactions were confirmed using FTIR and ¹³C NMR spectroscopy. The properties of these blends were studied in detail by varying the amount of compatibilizer, and the improved mechanical behaviour was correlated with the morphology with the help of scanning electron microscopy. Morphology studies also revealed the interfacial interaction in the blend containing grafted PBT. The improvement in the properties of these blends can be attributed to the effective interaction of grafted maleic anhydride groups with the amino group in PA66. The results indicate that PBT‐g‐MA acts as an effective compatibilizer for the immiscible blends of PBT and PA66. © 2000 Society of Chemical Industry     

Interfacial modification of high density polyethylene/glass fiber reinforced and non reinforced polyamide 66 blends

High density polyethylene (HDPE) and polyamide (PA66) are well known to be incompatible. An ionomer (Surlyn) was added as a compatibilizer to HDPE and glass fiber reinforced (HDPE/GFRPA66) and non‐reinforced (HDPE/PA66) blends. Two compositions were considered: 25/75 wt % and 75/25 wt %, with an emphasis on the former formulation. The influence of the compatibilizer on the rheology, thermal properties, and the morphology, as well as mechanical properties of the blends, was investigated using melt flow index measurements, DSC, scanning electron microscopy (SEM), and impact strength. The ionomer was found to be more effective as a compatibilizer with HDPE as a minor phase compared to the case when HDPE becomes the major phase. The results indicated that the interfacial properties of the blends were improved, with a maximum appearing at a critical concentration of the ionomer (7.5 vol %). At this level of compatibilization, SEM analysis revealed better interfacial adhesion and a finer dispersion. MFI results revealed a probable reaction between the amine groups of PA66 and the acid functions of the ionomer. The mechanical properties support the above results and showed that the addition of 25 wt % HDPE did not affect the properties of PA66 much and the presence of glass fiber did not hinder the effect of the compatibilizer. Only 20% decrease in notched Izod impact strength of the blends is observed at 7.5 vol % ionomer content, suggesting that the addition of 25 wt % of HDPE to PA66 is not detrimental at this level of compatibilization. The emulsification curve was established and revealed that, in terms of impact properties, the finer the particle size, the higher the impact strength corresponding to 7.5 vol % ionomer content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1748–1760, 2005     

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     

A quantitative estimation of the extent of compatibilization in heterogeneous polymer blends using their heat capacity increment at the glass transition

In this paper a new method based on the determination of heat capacity increment at the glass transition (ΔCp) is presented to quantify the effectiveness of compatibilizers for immiscible polymer blends. In order to show the validity of the method, two immiscible blends, polypropylene–poly(ethylene terephthalate) (PP–PET) and PP–polyamide‐6,6 (PP–PA66), and two compatibilizers, N, N‐dihydroxyethyl monomaleic amide–grafted PP (g–PP) alone and together with a phenolic resin (PR), were investigated. Scanning electron microscopy (SEM) observations prove that the two compatibilizer systems are both effective for compatibilizing the blends, and the combined use of g–PP and PR is more effective than g–PP alone. Modulated‐temperature differential‐scanning calorimetry (M‐TDSC) determinations reveal that the ΔCp varies with the extent of compatibilization. For the uncompatibilized blends, the ΔCp for the PET component in PP–PET or for the PA66 component in PP–PA66 was found to be almost unchanged. After compatibilization these quantities become smaller. Also, the combined use of g–PP and PR results in the smallest ΔCp values for both blends. This ΔCp change with different compatibilizers is in very good agreement with the corresponding morphological variation observed by SEM. Thus, ΔCp can be taken as a new parameter for quantifying the extent of compatibilization, since it is a direct measure of interfacial content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2868–2876, 1999     

Compatibilization of PVDF/PA6 Blend by the Addition of a Third Polymer PTFE

The compatibilization of poly(vinylidene fluoride) (PVDF) with polyamide 6(PA6, higher acrylonitrile content) blend was improved by adding poly(methyl methacrylate) (PTFE). It was confirmed by characterizing the mechanical and tribological properties of the blends. More homogeneous morphology was formed when PTFE was added into PVDF/PA6 blend, which was shown in scanning electron microscopy (SEM). The surface tension of blends was increased due to the higher polar surface tension of PTFE. As the content of PTFE was increased further, the tensile strength of the blend was slightly decreased.     

Morphology evolution of a thermotropic liquid‐crystalline polymer in a polyamide 6,6 matrix regulated by graphene

A two‐step process, thermotropic liquid‐crystalline polymer (TLCP) premixing with reduced graphene oxide (RGO) followed by blending with polyamide 6,6 (PA66), was used to prepare ternary TLCP/RGO/PA66 blends. The rheological behaviors, morphology, and mechanical properties of the blends were investigated. The results show that RGO migrated from the TLCP phase to the interface between the TLCP and PA66 phase during melt blending; this was due to a similar affinity of the RGO nanosheets to both component polymers. The dimensions of the dispersive TLCP domains were markedly reduced with the mounting RGO content; this revealed a good compatibilization effect of RGO on the immiscible polymers. The hierarchical structures of the TLCP fibrils were found in both the unfilled TLCP/PA66 blends and TLCP/RGO/PA66 blends. This supposedly resulted from the extensional and torsional action of unstable capillary flow. With the addition of RGO, the viscosities of the blends decreased further, and the fibrillation of TLCP and the mechanical performance of TLCP composites were both enhanced. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43735.     

Morphology,thermal behavior,and mechanical properties of PA6/UHMWPE blends with HDPE‐g‐MAH as a compatibilizing agent

A functionalized high‐density polyethylene (HDPE) with maleic anhydride (MAH) was prepared using a reactive extruding method. This copolymer was used as a compatibilizer of blends of polyamide 6 (PA6) and ultrahigh molecular weight polyethylene (UHMWPE). Morphologies were examined by a scanning electron microscope. It was found that the dimension of UHMWPE and HDPE domains in the PA6 matrix decreased dramatically, compared with that of the uncompatibilized blending system. The size of the UHMWPE domains was reduced from 35 μm (PA6/UHMWPE, 80/20) to less than 4 μm (PA6/UHMWPE/HDPE‐g‐MAH, 80/20/20). The tensile strength and Izod impact strength of PA6/UHMWPE/HDPE‐g‐MAH (80/20/20) were 1.5 and 1.6 times as high as those of PA6/UHMWPE (80/20), respectively. This behavior could be attributed to chemical reactions between the anhydride groups of HDPE‐g‐MAH and the terminal amino groups of PA6 in PA6/UHMWPE/HDPE‐g‐MAH blends. Thermal analysis was performed to confirm that the above chemical reactions took place during the blending process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 232–238, 2000     

Influence of in situ compatibilization on in situ formation of low‐density polyethylene/polyamide 6 blends by reactive extrusion

Low‐density polyethylene/polyamide 6 (LDPE/PA6) blends were in situ formed by reactive extrusion, in which in situ polymerization of ε‐caprolactam (CL) and in situ copolymerization of maleic anhydride grafted low‐density polyethylene (LDPE‐MA) and CL took place simultaneously. The latter reaction could be considered as in situ compatibilization, and the influence of in situ compatibilization on the morphologies, thermal properties, and rheological behaviors of the blends was investigated in this work. Scanning electron microscopy showed that the in situ compatibilization could dramatically reduce the dispersed phase sizes and narrow the size distribution. The thermal properties indicated that in differential scanning calorimetry (DSC) cooling scans, fractionated crystallization of the PA6 component was observed in all cases and was promoted with increasing the amount of LDPE‐MA. The DSC second heating scans showed the in situ compatibilization could stimulate the formation of the less stable γ‐crystalline form of PA6 in the blends. Dynamic rheological experiments revealed the in situ compatibilization had enhanced the viscosity, storage modulus, and loss modulus of the blend and reduce the corresponding slope values of the storage modulus and loss modulus. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

原位增容PA6/PE-HD共混物的性能研究

在双螺杆挤出机上通过原位增容反应挤出制备了聚酰胺6(PA6)/高密度聚乙烯(PE-HD)共混物。通过力学性能测试、扫描电子显微镜观察和Molau实验,研究了PE-HD含量对PA6/PE-HD共混物的力学性能和体系增容作用的影响。结果表明,PE-HD与马来酸酐(MAH)在挤出共混过程中原位生成了PE-HD-g-MAH,其对PA6/PE-HD共混物有较好的增容作用;PA6/PE-HD共混物的力学性能与界面形态均有较大改善,吸水率有所降低。     

Compatibilization of ethylene/maleic anhydride/glycidyl methacrylate terpolymer for poly(phenylene sulfide)/poly(amide‐66) blends

In this article, a terpolymer of ethylene, maleic anhydride, and glycidyl methacrylate (EMG) was used to enhance the compatibilization between poly(phenylene sulfide) (PPS) and polyamide‐66 (PA66). The mechanical properties, morphology, crystalline and melting behavior, and rheology of blends were discussed. The results showed that EMG was a good compatibilizer for PPS and PA66 through chemical reaction with them. The new generated polymer could prevent the aggregation of dispersed particles and reinforce the interface bonding. In addition, it could not only act as a nucleating agent for PA66 to refine its spherulites and improve its crystallinity but also promote the apparent viscosity of blends and enhance the non‐Newtonian behavior. The results will be useful to make high performance PPS/PA66 alloy with low cost and enlarge the application scope of PPS and PA66 resin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure-property relationships of microfibrillar reinforced blends of linear polycondensates

Binary microfibrillar reinforced composites are obtained by melt-blending of poly(ethylene terephthalate) (PET) and polyamide 6 (PA6), as well as polyamide 66 (PA66) and PA6 (both 40/60 by wt) in the presence of a catalyst, followed by cold drawing of the bristle to about 3.5 times and annealing at 220 or 240C. The blends are studied by X-ray diffraction, scanning electron microscopy (SEM), light microscopy and static mechanical testing. SEM and light microscopy reveal different blend morphologies due to differences in the miscibility of the homopolymers: the PA66/PA6 blend is morphologically more homogeneous, than the PET/PA6 blend. Annealing at 240C results in preservation of the high orientation of PET and PA66 while the PA6 portions of the two blends are partially disoriented, much more for the PET/PA6 blend as concluded from the X-ray data. Annealing at 240C suggest also transreactions leading to the in situ generation of block copolymers in addition to the generated ones during blend mixing in the extruder which improve the compatibility of the blend components. These physical and chemical changes affect the mechanical properties of the fibrillar reinforced blends and composites. The Young's moduli (E) and tensile strength ( σ t ) of the drawn blends are 5-6 and 7-9 times higher than those of the asextruded samples. Heat treatment at 220C results in a slight (for PA66/PA6) and stronger (for PET'PA6 blend) decrease of the σ t while E remains unchanged. A stronger decrease of E in both blends and of σ t in PA66/PA6 sample has been observed after annealing at 240C. Nevertheless, E and σ t of the last samples are about 3 times higher than those for the neat PA6.     

Injection moldability and properties of compatibilized PA6/LDPE blends

An ethylene‐acrylic acid copolymer (EAA), either alone or combined with a low molar mass bis‐oxazoline compound (PBO), has been used as a compatibilization promoter for blends of polyamide‐6 (PA6) with low‐density polyethylene (LDPE). The effect of compatibilization on blend processability in injection molding operations and on the properties of the molded specimens has been studied. In the absence of compatibilization, the injection molded articles were shown to have low‐quality surface appearance and poor mechanical properties. Both these characteristics were appreciably improved as a result of reactive compatibilization of the blends with EAA and, even more, with the EAA‐PBO couple. In fact, the finished articles prepared by injection molding of the quaternary blends were shown to possess good surface appearance, fine and stable morphology and satisfactory mechanical properties. The results confirm the conclusion of a previous study, i.e., that the PBO fourth component may promote the in situ formation of PA6‐g‐EAA copolymers, by reaction with both the functional groups of PA6 and the carboxyl groups of EAA. Polym. Eng. Sci. 44:1732–1737, 2004. © 2004 Society of Plastics Engineers.