Compatibilizing effect of styrene–maleic anhydride copolymer on the properties of polyamide‐6/liquid crystalline copolyester composites

Liquid crystalline polymer–polyamide‐6 (LCP/PA6) composites containing 20 wt % LCP content were compatibilized by a random styrene–maleic anhydride copolymer (RSMA). The blending was performed via extrusion followed by injection molding. The LCP employed was a commercial copolyester, Vectra A950. The dynamic mechanical (DMA), rheological, thermal, and mechanical properties as well as the morphology of the composites were studied. The DMA and rheological results showed that RSMA is an effective compatibilizer for LCP/PA6 blends. The mechanical measurements showed that the stiffness, tensile strength, and toughness of the in situ composites are generally improved with increasing RSMA content. However, these mechanical properties deteriorated considerably when RSMA content was above 10 wt %. The drop‐weight dart impact test was also applied to analyze the toughening behavior of these composites. The results show that the maximum impact force (F_max) and crack‐initiation energy (E_init) tend to increase with increasing RSMA content. From these results, it appeared that RSMA prolongs the crack‐initiation time and increases the energies for crack initiation and impact fracture, thereby leading to toughening of LCP/PA6 in situ composites. Finally, the correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1964–1974, 2000     

Microstructure and fracture behavior of (co)injection‐molded polyamide 6 composites with short glass/carbon fiber hybrid reinforcement

The mechanical and fracture properties of injection molded short glass fiber)/short carbon fiber reinforced polyamide 6 (PA 6) hybrid composites were studied. The short fiber composites of PA 6 glass fiber, carbon fiber, and the hybrid blend were injection molded using a conventional machine whereas the two types of sandwich skin–core hybrids were coinjection molded. The fiber volume fraction for all formulations was fixed at 0.07. The overall composite density, volume, and weight fraction for each formulation was calculated after composite pyrolysis in a furnace at 600°C under nitrogen atmosphere. The tensile, flexural, and single‐edge notch‐bending tests were performed on all formulations. Microstructural characterizations involved the determination of thermal properties, skin–core thickness, and fiber length distributions. The carbon fiber/PA 6 (CF/PA 6) formulation exhibits the highest values for most tests. The sandwich skin‐core hybrid composites exhibit values lower than the CF/PA 6 and hybrid composite blends for the mechanical and fracture tests. The behaviors of all composite formulations are explained in terms of mechanical and fracture properties and its proportion to the composite strength, fiber orientation, interfacial bonding between fibers and matrix, nucleating ability of carbon fibers, and the effects of the skin and core structures. Failure mechanisms of both the matrix and the composites, assessed by fractographic studies in a scanning electron microscope, are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 957–967, 2005     

UV老化对ZnO填充PA6/LGF复合材料性能的影响

用熔融共混法制备出长玻璃纤维(LGF)含量为30%的LGF增强尼龙6(PA6)/ZnO(PA6/LGF/ZnO)复合材料,并采用氙灯紫外(UV)老化法研究了ZnO含量为0%~8%及UV老化时间为0~800 h对复合材料力学性能和结晶性能的影响。结果表明,经UV辐照后,PA6/LGF/ZnO复合材料的拉伸强度升高,韧性下降,其中当ZnO添加量为6%时,复合材料在800 h老化后的拉伸强度和缺口冲击强度保留率较未添加ZnO的复合材料分别提高了5.39%和4.98%。SEM分析表明在UV老化过程中,LGF与PA6基体之间的界面并未受到明显破坏,老化主要集中发生在PA6基体上。随着老化时间的延长,PA6/LGF复合材料中的PA6出现UV交联而使其结晶度从26.19%降低至20.70%;对于ZnO含量为6%的PA6/LGF/ZnO复合材料,老化800 h后其结晶度仅从22.92%下降至21.34%,PA6/LGF/ZnO复合材料整体上的结晶性能趋于稳定。     

The influence of carbon black batches on the fracture behavior of glass fiber reinforced PA6/PA66 blends

The toughness behavior of 30 wt % glass fiber reinforced PA6/PA66 blends colored with different masterbatches containing carbon black (CB) was characterized by the instrumented Charpy impact test. Two different CB types with different particle diameters as well as two different polymers, PE and PA6, were used to prepare the masterbatches. The CB concentration was varied from 0 to 1.2 wt % in the compounds and all materials were examined dry and after water absorption. The toughness of the compounds significantly decreased when CB was incorporated. Moisture conditioning of the materials led to increased toughness and ductility but did not compensate for the negative influence of CB. Using PE as a masterbatch polymer succeeded in limiting the influence of CB on toughness whereas the largest particle diameter led to the highest reduction in toughness. By taking into account crack resistance curves, it could be shown that there is a significant change in crack propagation behavior when the concentration of the larger particle CB exceeds a certain level; this was ascribed to the existence of complex CB structures at this concentration. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

长玻璃纤维增强PA66复合材料的综合性能及其影响因素研究

利用定制的熔融浸渍装置制备了长玻璃纤维增强聚酰胺66(PA66/LGF)复合材料,并对其力学性能、界面黏结性等进行了表征,探讨了玻璃纤维含量、润滑剂含量、相容剂含量以及切粒长度等因素对复合材料性能的影响,得到了PA66/LGF复合材料优化的配方设计与切粒长度.结果表明,当玻璃纤维含量为43％(质量分数,下同)、切粒长度...     

In situ synthesis of bone‐like hydroxyapatite/polyamide 6 nanocomposites

BACKGROUND: Polymer/hydroxyapatite (HA) nanocomposites have emerged in recent years as a new class of biomaterials that can be used as artificial bone. Compared to pure HA or HA‐based bioceramics, and metallic implants, they exhibit good plasticity, improved toughness and good mechanical compatibility with natural bone. Compared to their microcomposite counterparts and the pristine polymer matrix, they show increased tensile strength and modulus, and enhanced bioactivity. RESULTS: In this study, polyamide 6 (PA6)/nanoscale HA (n‐HA) nanocomposites were prepared via in situ hydrolytic ring‐opening polymerization of ε‐caprolactam in the presence of newly synthesized n‐HA aqueous slurry. The synthesized n‐HA, which is similar to bone apatite in chemical composition, microscopic morphology and phase composition, dispersed uniformly in the composites even if its loading was up to 60 wt%. The PA6/n‐HA composites show a similarity to natural bone in chemical composition to a certain extent. Mechanical tests show that the composites are reinforced considerably by the incorporation of needle‐like n‐HA, and the composites have mechanical properties near to those of natural bone. CONCLUSION: The PA6/n‐HA nanocomposite with high n‐HA content shows a similarity to natural bone in terms of chemistry and mechanical properties. This makes it a possible candidate for biomaterials suitable for bone repair or fixation. Copyright © 2008 Society of Chemical Industry     

Synthesis of glass fiber‐multiwall carbon nanotube hybrid structures for high‐performance conductive composites

The conductive polyamide 66 (PA66)/carbon nanotube (CNT) composites reinforced with glass fiber‐multiwall CNT (GF‐MWCNT) hybrids were prepared by melt mixing. Electrostactic adsorption was utilized for the deposition of MWCNTs on the surfaces of glass fibers (GFs) to construct hybrid reinforcement with high‐electrical conductivity. The fabricated PA66/CNT composites reinforced with GF‐MWCNT hybrids showed enhanced electrical conductivity and mechanical properties as compared to those of PA66/CNT or PA66/GF/CNT composites. A significant reduction in percolation threshold was found for PA66/GF‐MWCNT/CNT composite (only 0.70 vol%). The morphological investigation demonstrated that MWCNT coating on the surfaces of the GFs improved load transfer between the GFs and the matrix. The presence of MWCNTs in the matrix‐rich interfacial regions enhanced the tensile modulus of the composite by about 10% than that of PA66/GF/CNT composite at the same CNT loading, which shows a promising route to build up high‐performance conductive composites. POLYM. COMPOS. 34:1313–1320, 2013. © 2013 Society of Plastics Engineers     

Enhancement of interlaminar fracture toughness of carbon fiber–epoxy composites using polyamide‐6,6 electrospun nanofibers

In this study, carbon fiber–epoxy composites are interleaved with electrospun polyamide‐6,6 (PA 66) nanofibers to improve their Mode‐I fracture toughness. These nanofibers are directly deposited onto carbon fabrics before composite manufacturing via vacuum infusion. Three‐point bending, tensile, compression, interlaminar shear strength, Charpy impact, and double cantilever beam tests are performed on the reference and PA 66 interleaved specimens to evaluate the effects of PA 66 nanofibers on the mechanical properties of composites. To investigate the effect of nanofiber areal weight density (AWD), nanointerlayers with various AWD are prepared by changing the electrospinning duration. It is found that the electrospun PA 66 nanofibers are very effective in improving Mode‐I toughness and impact resistance, compressive strength, flexural modulus, and strength of the composites. However, these nanofibers cause a decrease in the tensile strength of the composites. The glass‐transition temperature of the composites is not affected by the addition of PA 66 nanofibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45244.     

The Improvement of Compatibility in Glass Fiber Reinforced PA6/PP Blends

Abstract

Rheological properties (melt flow index and melt stability), mechanical properties (tensile strength, flexural strength and impact) of polyamide (PA6) polypropylene (PP) blends were investigated. Influence of potential compatibilizors: 4,4′-diphenyhnethane carbodiimide (OCDI), 4,4′-diphenylmethane bismaleimide (BMI) and 2,2′-(1,4-pheaylene)-bisoxazoline (OX) on mechanical properties and thermostability of initial and glass reinforced polymer blends was also investigated too. We tried to study the structure of glass fiber reinforced composites by mercury intrusion porosimitry. The influence of compatibilizors on molecular weight of PA6 was studied by GPC, on chemical structure of blends was investigated by NMR and IR-spectroscopy. Addition of OCDI and OX (chain extenders) preserves the product formation as the react with the active and carbonyl groups of PA6. BMI has lower reactivity. Grafting of BMI to PP chains improves compatibility in PA6/PP blend and increases PP adhesion to glass fiber.     

高含量玻璃纤维增强阻燃聚酰胺材料的制备与性能

采用双螺杆挤出机制备了聚酰胺6(PA6)/50%（质量分数,下同）玻璃纤维（GF）、PA66/50%GF、PA56/50%GF 3种高含量GF增强阻燃PA复合材料,对比研究了红磷、溴系、磷氮3种阻燃体系下复合材料的力学性能、阻燃性能和激光打标性能。结果表明,不同阻燃体系对复合材料的力学性能有明显影响,吸水平衡后,PA66复合材料的力学性能保持率最高;PA56复合材料在3种阻燃体系中均表现出比PA6、PA66复合材料更好的阻燃性能;红外激光和紫外激光的打标效果存在明显不同,而在阻燃体系和激光光源相同的条件下,PA6、PA66和PA56 3种PA复合材料的激光打标效果没有明显差异。     

Ultrahigh Flowability and Excellent Mechanical Performance of Glass Fiber/PA6 Composites Prepared by Hyperbranched Polymers

Lightweighting of automotives is crucial for the decrease of fuel and energy consumption, as well as CO₂ emission and environmental pollution. Polymer composites, especially the high strength glass fiber/polyamide (GF/PA) composites, have great potential in lightweight; however, they have not been universally accepted due to their insufficient performance. Here, a stearate-ended hyperbranched polyester (HBP-12-n) is designed and high-performance GF/PA6 composites with high GF content are prepared. The flowability of the composites can be further increased by combining carboxyl-ended hyperbranched polymer (HyPer C181) with HBP-12-n. Compared with unmodified GF/PA6 composites, the melt flow index (MFI) can be increased remarkably to 587% by adding a 0.7 wt% mixture of HBP-12-75 and HyPer C181, and the strength and toughness remain competitive. The simultaneous improvement in MFI and impact strength of GF/PA6 composites is the first discovery of this kind, and a synergistic mechanism of amphiphilic bridging-deformation slipping-interfacial strengthening of hyperbranched polymers is proposed to account for this phenomenon. This work provides a simple strategy to fabricate GF/PA6 composites with the extensive application for automotive parts and has great prospects in making automotives lightweight and reduction of CO₂ emissions.     

Crystallization behavior of PP/PP‐g‐MAH/GFR PA66 blends: Establishment of their continuous‐cooling‐transformation of relative crystallinity diagrams

Polypropylene/polypropylene‐grafted‐maleic anhydride/glass fiber reinforced polyamide 66 (PP/PP‐g‐MAH/GFR PA 66) blends‐composites with and without the addition of polypropylene‐grafted‐maleic anhydride (PP‐g‐MAH) were prepared in a twin screw extruder. The effect of the compatibilizer on the thermal properties and crystallization behavior was determined using differential scanning calorimetry analysis. The hold time was set to be equal to 5 min at 290°C. These conditions are necessary to eliminate the thermomechanical history in the molten state. The crystallization under nonisothermal conditions and the plot of Continuous‐Cooling‐Transformation of relative crystallinity diagrams of both PP and PA 66 components proves that PP is significantly affected by the presence of PP‐g‐MAH. From the results it is found that an abrupt change is observed at 2.5 wt % of PP‐g‐MAH as a compatibilizer and then levels off. In these blends, concurrent crystallization behavior was not observed for GFR PA66. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1620–1626, 2007     

玻璃纤维增强尼龙66改性研究进展

阐述了玻璃纤维增强尼龙66在增韧改性、阻燃改性、耐溶剂改性、耐磨改性、界面改性、复合改性和制备工艺改进等方面的研究进展。指出玻璃纤维增强尼龙66目前常用的增韧方法是与弹性体和高韧性聚烯烃共混,而阻燃改性的有效手段是添加微胶囊化红磷和P-N型阻燃剂。     

啮合同向双螺杆挤出机的螺杆构型对玻璃纤维增强PA66/PA6合金力学性能的影响

研究了在加工温度、螺杆转速、喂料速度等加工工艺相同的情况下,不同螺杆构型对玻璃纤维增强PA66/PA6合金产品力学性能的影响。结果表明：合理的螺杆构型可以得到力学性能优良的玻璃纤维增强PA66/PA6合金产品。通过对螺杆构型的调整,玻璃纤维增强PA66/PA6合金产品的拉伸强度、弯曲强度、冲击强度分别由56MPa、100MPa、64J/m提高至169MPa、238MPa、136J/m。     

Effect of transfer film on tribological behavior of polyamide 66‐based binary and ternary nanocomposites

BACKGROUND: In a polymer–metal sliding system, the formation and performance of the transfer film have important effects on the tribological behavior of the polymer. In order to reveal the wear mechanism of polyamide 66 (PA 66) and its composites consisting of styrene–(ethylene/butylene)–styrene triblock rubber grafted with maleic anhydride (SEBS‐g‐MA) particles and organoclay nano‐layers, the tribological behavior and transfer films of polyamide 66 and its composites were investigated under dry sliding. RESULTS: The incorporation of SEBS‐g‐MA rubber particles reduces the wear mass loss of PA 66, while the addition of organoclay nano‐layers increases the wear mass loss. The transfer films formed by neat PA 66 and PA 66/organoclay binary nanocomposite include a dark portion and bright portion. In the dark portion, the transfer film is thicker; in the bright portion, the steel ring surface is exposed. The transfer film formed by PA 66/SEBS‐g‐MA/organoclay ternary nanocomposite is thinner and more uniform than the transfer films formed by the other materials. CONCLUSION: When SEBS‐g‐MA rubber particles and organoclay nano‐layers are added simultaneously to PA 66, the wear resistance of PA 66 can be improved markedly. The main reason is that PA 66/SEBS‐g‐MA/organoclay ternary nanocomposite can form a thin and uniform transfer film on the steel ring surface. Copyright © 2008 Society of Chemical Industry     

Preparation and properties of polyamide‐6‐based thermoplastic laminate composites by a novel in‐mold polymerization technique

In this work, a method for preparation of polyamide‐6 (PA6) based laminates reinforced by glass fiber‐ (GFL) or polyamide‐66 (PA66) textile structures (PL) via reactive injection molding is disclosed. It is based on in‐mold anionic polymerization of ε‐caprolactam carried out at 165°C in the presence of the respective reinforcements performed in newly developed prototype equipment whose design concept and operation are described. Both composite types were produced for reaction times of 20 min, with conversion degrees of 97–99%. Initial mechanical tests in tension of GFL samples displayed almost twofold increase of the Young's modulus and stress at break values when compared with the neat anionic PA6. The improvement was proportional to the volume fraction V_f of glass fiber fabric that was varied in the 0.16–0.25 range. A 300% growth of the impact strength was registered in PL composites with V_f of PA66 textile of 0.1. Removing the surface finish of the latter was found to be a factor for improving the adhesion at the matrix–fiber interface. The mechanical behavior of GFL and PL composites was discussed in conjunction with the morphology of the samples studied by optical and electron microscopy and the matrix crystalline structure as revealed by synchrotron X‐ray diffraction. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40083.     

Toughness of nanoscale and multiscale polyamide‐6,6 composites

Fracture initiation and fracture propagation toughening (R‐curve behavior) of polyamide 6,6 (PA‐66) polymers with different types of layered silicate clay having nanoscale (fully dispersed) or multiscale (mixed nanoscale/microscale) structure were studied. These results were compared to fracture data for conventional kaolin clay particulate reinforcements and a PA‐66 polyblend containing rubber and rigid poly(styrene‐co‐acrylonitrile) particulates. The stiffness increase due to the intercalated clay was the same as would be predicted by classical models for conventional elongated reinforcements at the same volume fraction level. The special benefit of the nanoscale reinforcement derived from their high surface area of contact with the matrix. Toughness in layered silicate clay composites was enhanced by better dispersion of the clay, by exfoliation of the clay layers, and by a stronger clay/matrix interface. A multiscale microstructure was found to be the more desirable microstructure, combining toughness from the nanodispersed clay with resistance curve behavior from the micrometer‐sized particulates. Fracture toughness was proportional to the crack‐tip plastic zone size at fracture, indicating that the clay reinforcements, by influencing shear deformation in the crack tip region, played an important role in promoting toughness. There was indirect evidence for the formation of a zone of damage within the crack‐tip plastic zone that could explain why toughness was not optimal.     

Microstructure and mechanical behavior of polyamide 66‐precipitated calcium carbonate composites: Influence of the particle surface treatment

The effects of interfacial adhesion strength on the mechanical behavior of composites of polyamide 66 and precipitated calcium carbonate (CaCO₃) particles have been investigated. The 50 nm average diameter particles have been surface‐treated using two kinds of coupling agent having various affinities with respect to the matrix. The surface‐modified particles have been incorporated into the polyamide matrix via melt processing. Tensile and impact tests, associated with dynamical mechanical analysis, have been performed on injection‐molded samples. The structural characterization of the specimens has been carried out using differential scanning calorimetry and wide‐angle X‐ray scattering. It is observed that the matrix structure is roughly insensitive to the surface treatment, despite a weak nucleating effect of the filler particles. In contrast, the particle surface treatment strongly influences the particle dispersion in the polymer matrix. Although dispersion was not optimized, the elastic properties of the reinforced polyamide increase with the CaCO₃ content, below as well as above the glass transition temperature. Impact toughness decreases for CaCO₃ weight fraction greater than 5%. Scanning electron microscopy investigation reveals that the interfacial adhesion affects local deformation processes, such as debonding and fibrillation of the polymer matrix around the particles, during the macroscopic deformation of the composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 989–999, 2006     

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.     

Mechanical and tribological properties of PA66/PPS blend. III. Reinforced with GF

Based on previous work, 70 vol % PA66/30 vol % PPS blend was selected as a matrix, and the PA66/PPS blend reinforced with different content of glass fiber (GF) was prepared in this study. The mechanical properties of PA66/PPS/GF composites were studied, and the tribological behaviors were tested on block‐on‐ring sliding wear tester. The results showed that 20–30 vol % GF greatly increases the mechanical properties of PA66/PPS blend. When GF content is 20 vol %, the friction coefficient of composite is the lowest (0.35), which is decreased by 47% in comparison with the unfilled blend. The wear volume of the GF‐reinforced PA66/PPS blend composite decreases with the increase of GF content. However, the wear‐resistance is not apparently improved by the addition of GF in the experimental range for comparison with unfilled PA66/PPS blend. The worn surface and the transfer film on the counterface were examined by scanning electron microscopy (SEM). The observations revealed that the friction coefficient of composite depends on the formation and development of a transfer film. The wear mechanism involves polymer matrix wear and fiber wear. The former consists of melting wear and plastic deformation of the matrix, while the latter includes fiber sliding wear, cracking, rupturing, and pulverizing. The contributions of the matrix wear and the fiber wear determine the ultimate wear volume of PA66/PPS/GF composite. In addition, the abrasive action caused by the ruptured glass fiber is also a very important factor. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 523–529, 2006