Thermal and flow property–morphology relationship of sugarcane bagasse fiber‐filled polyamide 6 blends

The structure–property relationship of sugarcane bagasse fiber‐filled polyamide 6 blends at different blend compositions has been investigated. Blends were prepared in the composition of wt % PA6/wt % bagasse as follows: 98/2, 95/5, and 90/10 for three fiber length ranges (<100, <250, and <500 μm) using a twin‐screw extruder. Thermal properties were evaluated by measuring the glass transition temperature T_g, enthalpy of fusion ΔH_f, crystallinity X_c and thermogravimetry, TG. Results showed that T_g of the composites changed with change in fiber loading and length. The X_c as well as ΔH_f of the blends reduced to almost half its value for the neat PA6. The thermogravimetric curves TG showed that the thermal stability of the composites was lower than that of the neat PA6. Rheological properties were studied as a function of fiber loading, fiber length, shear rate, and temperature. The viscosity of composites increased with increasing fiber loading and length at low shear rates but decreased below that of neat PA6 at high shear rates. It was also found to be temperature sensitive, and influenced by fiber lengths particularly at higher temperatures. The morphology of the blends was studied using a Leica laser scanning confocal microscopy at two different regions: at the wall, and the core. The micrographs of the blends showed that fibers present in the form of bundles were found at the wall of the extrudates and increased in volume with increase in both length and concentration, at the same temperature and shear stress. In the core region, there is laminar flow, presenting striation morphology, with the omnipresent bundles of fibers dispersed in the matrix. At higher shear rates, the bundles were pushed to the wall. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3744–3754, 2004     

Thermal analysis of polyamide blends as obtained by reactive melt-extrusion: Influence of blend composition on crystallization and melting behavior

Polyamide blends composed of PA 46 and PA 6I were melt-mixed using a double-screw extruder, and the obtained compounds were subsequently processed by injection molding. The blend materials obtained were found to have undergone transamidation processes during the extrusion and injection-molding operations which alter the crystallization and melting behavior. The variation in thermal behavior is strongly dependent on the change in the average sequence length of the crystallizable component in the copolymer formed; it is affected by the compounding and processing conditions and by the blend composition. The influence of every melt-processing step on the crystallization and melting behavior of the blends was investigated by thermal analysis using extruded, injection-molded, and solution-prepared blends. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 573–580, 1997     

Mechanical and thermal characteristics and morphology of polyamide 6/isotactic polypropylene blends in the presence of a β‐nucleating agent

The mechanical and thermal characteristics and morphology of polyamide 6 (PA6)/isotactic polypropylene (iPP) blends (10/90 w/w) prepared with different processing procedures and incorporated with an aryl amide nucleating agent, a kind of β‐nucleating agent (β‐NA) for iPP, were investigated. The yield strength and flexural modulus of the blends decreased as β‐NA was introduced into the blends, whereas the impact strength and elongation at break improved. The crystalline structures of the blends closely depended on (1) the processing conditions and (2) competition between the β‐nucleating effect of β‐NA and the α‐nucleating effect of PA6 for iPP. Scanning electron microscopy, differential scanning calorimetry, and X‐ray diffraction were adopted to reveal the microstructures of the blends. At a low β‐NA content (<0.1 wt %), the α‐phase iPP dominated the blends, whereas the relative content of the β‐phase iPP increased remarkably when the β‐NA content was not less than 0.1 wt %. The processing conditions also showed profound influences on the supermolecular structures of iPP; this resulted in different mechanical properties of the blends. As for PA6, the crystallization behavior and crystalline structure did not exhibit obvious changes, but PA6 did play an important role in the epitaxial crystallization of iPP on PA6. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

In situ ester–amide exchange reaction between polyamide 6 and ethylene‐vinyl acetate rubber during melt blending

The ester–amide exchange reaction between polyamide 6 (PA6) and ethylene‐vinyl acetate rubber (EVM) with dibutyltin oxide (DBTO) as a catalyst took place during melt blending, leading to the formation of PA6‐grafted EVM copolymer (EVM‐g‐PA6) and acetamide‐terminated PA6. The exchange reaction extent, expressed by the percentage content of the acetate groups taking part in the exchange reaction, was 5.9 mol %, and the yield of EVM‐g‐PA6 copolymer was 6.8 wt % for PA6/EVM/DBTO (60/40/1) blend at 230°C for 60 min. The number‐average molecular weight of PA6 branches in EVM‐g‐PA6 was ～278 g/mol as evaluated from nuclear magnetic resonance spectra. The reaction kinetic parameters were calculated according to a second‐order reversible reaction mechanism. The rate constant was dependent on the catalyst concentration, PA6/EVM ratio, and shearing conditions. In this article, the characterized ester–amide exchange reaction between PA6 and EVM will guide the fabrication of novel EVM‐based graft copolymers and high‐performance PA6/EVM thermoplastic elastomers for engineering applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40272.     

Compatibility effect of radiation‐grafting‐functionalized styrene–butadiene–styrene on polyamide 6/styrene–butadiene–styrene blends

Styrene–butadiene–styrene (SBS) was grafted with dibutyl maleate (DBM), methacrylic acid (MAA), or maleic anhydride (MAH) by ⁶⁰Co γ‐rays. The grafted SBS was blended with polyamide 6 (PA6). The compatibility of the PA6/SBS blends was studied with scanning electron microscopy and rheological measurements. The results showed significant improvement in the compatibility of PA6 blended with MAH‐ or MAA‐grafted SBS, with the former being more effective, whereas grafting DBM was ineffective in this respect. Mechanisms of the compatibility enhancement and ineffectiveness are discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The reactive compatibilization effect of copolymer macroactivator for immiscible anionic polyamide 6/polystyrene blends via in situ polymerization

In this article, a novel method has been successfully developed to prepare the anionic polyamide 6/polystyrene (APA6/PS) blends. The macroactivator P(St‐co‐IEM) was synthesized by the free radical polymerization of 2‐isocyanatoethyl methacrylate and styrene (St), then the graft copolymer of PS and APA6 (PS‐g‐APA6) can be obtained by the anionic polymerization of ɛ‐caprolactam activated by the macroactivator P(St‐co‐IEM). The X‐ray diffraction analysis, differential scanning calorimetry, scanning electron microscopy analysis, contact angle measurement, water absorption measurement, molau test, thermogravimetric analysis, and mechanical properties test were performed separately to study the effects of P(St‐co‐IEM) on crystallinity, morphology, water resistance, thermal stability, and mechanical properties. The results indicate the synthesis of macroactivator can promote the formation of the γ‐phase. Moreover, it can improve the interfacial compatibility, water resistance, thermal stability, and toughness. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46302.     

Synthesis and characterization of heat‐resistant N‐phenylmaleimide–styrene–maleic anhydride copolymers and application in acrylonitrile–butadiene–styrene resin

The heat‐resistant copolymer of N‐phenylmaleimide (NPMI)–styrene (St)–maleic anhydride (MAH) was synthesized in xylene at 125°C with di‐tert‐butyl diperoxyterephthalate as an initiator. The characteristics of the copolymer were analyzed by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR), gel permeation chromatography, and elemental analysis. The ¹³C‐NMR results show that the copolymer possessed random sequence distribution; this was also supported by the differential scanning calorimetry experiment, in which a single glass‐transition temperature (T_g) of 202.3°C was observed. The thermal stability and degradation mechanism of the copolymer were investigated by thermogravimetric analysis. Using the Kissinger equation and Ozawa equation, we proved a nucleation controlling mechanism with an apparent activation energy of 144 kJ/mol. Blends of acrylonitrile–butadiene–styrene with the NPMI–St–MAH copolymer with various contents were prepared with a twin‐screw extruder processes. The mechanical and thermal properties of the materials, such as the tensile and flexural strength, T_g's, and Vicat softening temperatures, were all enhanced with the addition of the modifier, whereas the melt flow index decreased. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal behavior and morphology of polyamide 6 based multicomponent blends

The thermal behavior and morphology of multicomponent blends based on PA6, polyamide 6 (PA6)/styrene–acrylonitirle copolymer (SAN), PA6/acrylonitrile–butadiene–styrene terpolymer (ABS), and their compatibilized blends with styrene–acrylonitrile–maleic anhydride copolymer (SANMA) were studied using DSC and SEM. The blends were prepared in a twin‐screw extruder under similar processing conditions, keeping the PA6 content fixed at 50 wt %. It was found that, in all the blends, the second component had a nucleating effect and improved the overall degree and rate of crystallization of PA6, whereas addition of a compatibilizer slightly diminished these effects and resulted in significant changes in the blend morphology. The nucleating effect and consequent changes in the crystallization behavior was attributed to the presence of SAN, which is a common component in all the blends. The T_g of PA6 in the blends with a cocontinuous morphology, due to the connectivity between the phases, is higher than in the blends with a disperse‐type morphology. The compatibilized blends have a lower crystallization rate and nucleation ability with a cocontinuous morphology, whereas the uncompatibilized blends have a higher crystallization rate with a higher nucleation ability and a disperse and/or a coarse cocontinuous morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2753–2759, 2002     

Synthesis of high‐solid‐content,acrylic pressure‐sensitive adhesives by solvent polymerization

In this study, we prepared high solid content (SC), solvent‐based, acrylic pressure‐sensitive adhesives (PSAs) with n‐dodecyl mercaptan as a chain‐transfer agent (CTA) and studied the crosslinking reactions between the crosslinker and the acrylic PSAs. Acrylic PSAs were prepared from 2‐ethyl hexyl acrylate, acrylic acid (AA), and 2‐azobisisobutyronitrile with a solution polymerization process. The results show AA resulted in an effective molecular weight in the acrylic PSAs, as it improved the hydrophilicity with increasing peel strength of the acrylic PSAs. As for the high SC, the molecular weight and system viscosity decreased through the addition of CTA. At a constant AA amount, the addition of CTA decreased the molecular weight and increased the hydrophobicity of the acrylic PSAs; this decreased the peel strength of the acrylic PSAs on the glass. Furthermore, the addition of CTA decreased the molecular weight and improved the acrylic PSAs' surface morphologies and optical properties. The acrylic PSAs produced in this study could meet production needs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46257.     

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.     

Preparation and properties of halogen‐free flame‐retarded phthalonitrile–epoxy blends

Halogen‐free flame‐retarded blends composed of 2,2‐bis[4‐(3,4‐dicyanophenoxy) phenyl] propane (BAPh) and epoxy resin E‐44 (EP) were successfully prepared with 4,4′‐diaminodiphenyl sulfone as a curing additive. The structure of the copolymers was characterized by Fourier transform infrared spectroscopy, which showed that epoxy groups, a phthalocyanine ring, and a triazine ring existed. The limiting oxygen index values were over 30, and the UL‐94 rating reached V‐0 for the 20 : 80 (w/w) BAPh/EP copolymers. Differential scanning calorimetry and dynamic rheological analysis were employed to study the curing reaction behaviors of the phthalonitrile/epoxy blends. Also, the gelation time was shortened to 3 min when the prepolymerization temperature was 190°C. Thermogravimetric analysis showed that the thermal decomposition of the phthalonitrile/epoxy copolymers significantly improved with increasing BAPh content. The flexible strength of the 20:80 copolymers reached 149.5 MPa, which enhanced by 40 MPa compared to pure EP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synergistic mechanical response of Nylon 6/Trogamid® T blends

Blends of semicrystalline Nylon 6 with a varying ratios of amorphous Nylon are studied for their morphological, thermal, dielectric, and mechanical behavior. Thermal analysis indicated a compositional dependant decrease in the melting and crystallization temperatures of Nylon 6. The blends exhibited a single compositional dependant glass transition temperature in dynamic mechanical thermal analysis and dielectrical relaxation spectroscopy over entire mixing ratio indicating miscibility between the blend components. The values of flexural modulus and tensile modulus of the blends are found to increase without significant loss in the impact properties. The water absorption of the blends is also lower than the values calculated by rule of mixtures. The observed synergistic behavior of the mechanical properties of the blends is indicative of presence of strong interactions in the blends components. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Gasoline permeation behavior and mechanical properties of polyamide 6/nanoclay,polyamide 6/PE‐g‐maleic anhydride blend,and polyamide 6/PE‐g‐maleic anhydride/clay nanocomposite

In this article, polyamide 6 (PA6)/clay nanocomposites, PA6/polyethylene grafted maleic anhydride (PE‐g‐MA) blends, and PA6/PE‐g‐MA/clay nanocomposites were prepared and their gasoline permeation behavior and some mechanical properties were investigated. In PA6/clay nanocomposites, cloisite 30B was used as nanoparticles, with weight percentages of 1, 3, and 5. The blends of PA6/PE‐g‐MA were prepared with PE‐g‐MA weight percents of 10, 20, and 30. All samples were prepared via melt mixing technique using a twin screw extruder. The results showed that the lowest gasoline permeation occurred when using 3 wt % of nanoclay in PA6/clay nanocomposites, and 10 wt % of PE‐g‐MA in PA6/PE‐g‐MA blends. Therefore, a sample of PA6/PE‐g‐MA/clay nanocomposite containing 3 wt % of nanoclay and 10 wt % of PE‐g‐MA was prepared and its gasoline permeation behavior was investigated. The results showed that the permeation amount of PA6/PE‐g‐MA/nanoclay was 0.41 g m^?2 day^?1, while this value was 0.46 g m^?2 day^?1 for both of PA6/3wt % clay nanocomposite and PA6/10 wt % PE‐g‐MA blend. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40150.     

Dielectric studies of hyperbranched aromatic polyamide and polyamide‐6,6 blends

The objective of this work was to study the interactions between polyamide‐6,6 (PA‐6,6) and hyperbranched (HB) polyamide with different functional end groups. The investigation focused on the thermal, dielectric, and viscoelastic properties of two kinds of HB polyamides, with amine and alkyl end groups, prepared by a one‐pot process, in a polyamide‐6,6 matrix. Thermal analysis (by TGA and DSC) allowed us to observe decomposition and glass‐transition temperatures of these polymers. The melting point, crystallization temperature, and crystallinity ratio remained practically independent of HB content. Dielectric relaxation spectroscopy (DRS) showed two secondary relaxation (γ and β) and one primary (α) relaxation in the HB polymers and in the blends similar to those observed in polyamide‐6,6 with comparable activation energies and distribution parameters. An increase of the glass‐transition temperature was observed, showing a reinforcement of the polymer matrix and a decrease of the molecular mobility of the polyamide chains when the percentage of amine‐terminated HB polyamide increased in the matrix. DRS results found on the alkyl‐terminated HB polymer blend were indistinct from those of the polyamide‐6,6 matrix. Viscoelastic experiments confirmed the results observed in DRS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1522–1537, 2005     

Compatibilized blends of PVC/PA12 and PVC/PP containing poly(lauryl lactam‐block‐caprolactone)

Specially designed block copolymers have played a role as compatibilizing agents in the system of immiscible polymer blends. We applied lauryl lactam (LA)–caprolactone (CL) block copolymer [P(LA‐b‐CL)] as a compatibilizing agent for immiscible poly(vinyl chloride) (PVC) blends with various polymers. These blends possess high thermal performance and toughness. We investigated the effect of P(LA‐b‐CL) as a compatibilizing agent for immiscible PVC blends with poly(ω‐lauryl lactam) [polyamide 12 (PA12)]. We also described the invention of a new compatibilizing agent system involving P(LA‐b‐CL) for PVC/polypropylene (PP) blends. The mechanical and thermal properties of (1) PVC/PA12 blend compatibilized with P(LA‐b‐CL) and (2) PVC/PP blend compatibilized with P(LA‐b‐CL)/PA12/maleic anhydride–modified PP were both enhanced. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1983‐1992, 2004     

Bio-based transparent polyamide 10T/10I/1012 with high performance

Transparent polyamide (TPA) is a type of optically transparent material with high performance, and poly(decamethylene terephthalamide) (PA10T) is an emerging bio-based opaque polyamide. With the purpose of preparing bio-based and low-cost TPA based on PA10T, we chose dodecanedioic acid and isophthalic acid as comonomers, and successfully obtained a series of transparent PA10T/10I/1012. The basic properties of these copolyamides were characterized by intrinsic viscosity measurement, Fourier transform infrared spectrometer, proton nuclear magnetic resonance, X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, ultraviolet–visible spectrophotometer, solvent resistance test, water absorption measurement, and tensile measurement. Results show that PA10T/10I/1012 copolymers are amorphous and have high optical transparency. Moreover, these copolymers exhibit high thermal stability, low water absorption, and good solvent resistance, and they also show better mechanical properties compared to some commercial TPAs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 136, 47305.     

Properties of crosslinked polyurethanes obtained by acrylic side‐group polymerization and of their blends with various plant oils

Novel polyurethane elastomers have been developed to incorporate plant oil into their matrix. Bisphenol A glycerolate diacrylate was used as a chain extender for the polyurethane prepolymer obtained from poly(tetramethylene oxide) glycol and 1,6‐hexane diisocyanate. The curing of the polyurethane acrylate matrix in the presence of the plant oil results in a network matrix which includes renewable resources in their structure. The effects of the inclusion of different vegetable oil (such as soybean oil, rapeseed oil, cotton oil, or sunflower oil) into the crosslinked polyurethane acrylates matrix were studied by evaluating various properties of the films such as the thermal behavior, the tensile properties, and the surface properties. The increases in chain extender content determine an increase of the thermal stability (the 10% weight loss decomposition temperatures increase from 325 to 375°C) and mechanical strength (from 3 to 9 MPa). Contact angle measurements have shown that the hydrophobic property of the films surface slightly increased with the incorporation of plant oil into the crosslinked polyurethane matrix. In addition, polyurethane/plant oil blends exhibit enhanced mechanical strength (from 3 to 9.8 MPa), as well as an increased roughness reaching a maximum average (113 nm) in the case of cotton oil. All polyurethane/plant oil blend present higher values for glass transition temperature and slightly enhanced values for thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Kinetics of the in situ polymerization and in situ compatibilization of poly(propylene) and polyamide 6 blends

In previous articles, we reported on a novel reactive extrusion process to obtain a compatibilized blend of polymer A and polymer B. It consisted in polymerizing the monomer of polymer A in the presence of polymer B. A fraction of the latter contained initiating sites from which the polymerization of monomer A took place. As such, both polymer A and a graft copolymer of polymer A and polymer B were formed in the process. That process was called in situ polymerization and in situ compatibilization of polymer blends. Its feasibility was illustrated for in situ polymerized and in situ compatibilized poly(propylene) and polyamide 6 (PP/PA6) blends. The latter were prepared by activated anionic polymerization of ?‐caprolactam (CL) in the presence of PP in a batch mixer and a twin‐screw extruder, respectively. A fraction of the PP contained isocyanate groups from which PA6 grafts were formed. Sodium caprolactam (NaCL) was used as the catalyst and a diisocyanate compound was used as the activator. In this study, we report on the effects of various parameters on the kinetics of the anionic polymerization of CL in the presence of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1498–1504, 2004     

Preparation of highly thermally conducting polyamide 6/graphite composites via low‐temperature in situ expansion

Highly thermally conducting polyamide 6 (PA6) composites with high loadings of low‐temperature expandable graphite (LTEG) were prepared by an in situ exfoliation melting process, and the thermal conductivity of the composites was measured by a hot‐disk method. A two‐point method was applied to evaluate the electrical conductivity of the composites with various graphite loadings, and the thermal percolation was observed in the vicinity of the electrical percolation threshold concentration. Dynamic rheology analysis was used to define the geometric change caused by the interconnection of the in situ exfoliated graphite flakes. X‐ray diffraction measurement confirmed that the exfoliation of LTEG was crucial to the overall thermal conductivity of the composites. Dynamic mechanical analysis revealed that the incorporation of LTEG significantly improved the damping properties of PA6. Thermogravimetric analysis and differential scanning calorimetry measurements were applied to study the thermal properties of the investigated PA6/LTEG composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39596.     

Poly(decamethylene terephthalamide) copolymerized with long‐chain alkyl dodecanedioic acid: Toward bio‐based polymer and improved performances

Poly(decamethylene terephthalamide) (PA10T), a bio‐based high‐performance semi‐aromatic polyamide, has been commercialized in recent years. However, there still are some weaknesses restricting its application range, such as narrow melt processing window and low ductility. In this study, we chose dodecanedioic acid (a potential bio‐based raw material) as the comonomer to prepare copolyamides [poly(decamethylene terephthalamide/decamethylene dodecanediamide), PA10T/1012] for solving these problems. The basic properties of these copolyamides were characterized by viscosity measurement, Fourier transform infrared spectrometer, proton nuclear magnetic resonance, wide‐angle X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and tensile measurement. Results show that, compared to PA10T, PA10T/1012 exhibits wider melt processing window and more outstanding elongation at break. Meanwhile, PA10T/1012 is still qualified for high temperature resistant material. Furthermore, T_g, T_d,5%, T_d,10%, and T_d,max of PA10T/1012 show a linear dependence on 1012 content, which is helpful to design new bio‐based copolyamides for meeting the needs of various occasions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46531.