Measurement and numerical simulation of three‐dimensional fiber orientation states in injection‐molded short‐fiber‐reinforced plastics

To determine three‐dimensional fiber orientation states in injection‐molded short‐fiber composites, a confocal laser scanning microscope (CLSM) is used. Since the CLSM optically sections the specimen, more than two images of the cross sections on and below the surface of the composite can be obtained. Three‐dimensional fiber orientation states can be determined by using geometric parameters of fiber images obtained from two parallel cross sections. For experiments, carbon‐fiber‐reinforced polystyrene is examined by the CLSM and geometric parameters of fibers on each cross‐sectional plane are measured by an image analysis. In order to describe fiber orientation states compactly, orientation tensors are determined at different positions of the prepared specimen. Three‐dimensional orientation states are obtained without any difficulty by determining the out‐of‐plane angles utilizing fiber images on two parallel planes acquired by the CLSM. Orientation states are different at different positions and show the shell–core structure along the thickness of the specimen. Fiber orientation tensors are predicted by a numerical analysis and the numerically predicted orientation states show good agreement with measured ones. However, some differences are found at the end of cavity. They may result from the fountain flow effects, which are not considered in the numerical analysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 500–509, 2003     

Influence of different compatibilizers on the morphology and properties of PA6/PET/glass fiber composites

Three kinds of compatibilizers, ethylene–ethyl acrylate copolymer (EEA), ethylene–ethyl acrylate–glycidyl methacrylate copolymer (EAG), and ethene–maleic anhydride–glycidyl methacrylate copolymer (EMG), were introduced to PA6/PET/GF blends for the first time to study the effect of different compatibilizers on composite. EEA, EAG, and EMG showed different effect on the properties of PA6/PET/GF blends. An observation of the GF–resin interface by scanning electronic microscope indicated EAG and EMG enhanced the adhesion of resin to GF, while EEA exhibited no improvement. Differential scanning calorimetry analysis showed that both EMG and EAG increased the degree of crystallinity of the PA6/PET/GF blends, whereas EEA declined. According to dynamic mechanical analysis, EAG, and EMG remarkably increased the storage modulus of composites. For the composites at a given GF content of 30 wt %, EMG increased the tensile strength from 140.6 to 156.3 MPa. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46429.     

Evaluation of processing effects in injection‐molded amorphous and crystalline thermoplastics using an excimer laser

The ablation behavior of amorphous [polystyrene (PS), polycarbonate (PC)] and crystalline [PET, glass‐filled poly(butylene terephthalate) (PBT)] polymers by 248‐nm KrF excimer laser irradiation were investigated for different injection‐molding conditions, namely, injection flow rate, injection pressure, and mold temperature, as a possible method for evaluating processing effects in the specimens. For this purpose, dumbbell‐shaped samples were injection‐molded under different sets of processing conditions, and weight loss measurements were carried out for the different injection‐molding conditions. Some of the crystalline (PET) samples were annealed at different annealing times and temperatures. For PET, the weight loss decreased with increasing mold temperature and remained insensitive to injection flow rate. Annealing time and temperature significantly reduced weight loss in PET. For PBT, the weight loss due to laser ablation decreased with increasing material packing due to pressure, and it also showed some sensitivity to flow rate variation. The major effect was seen with glass‐filled PBT samples. The weight loss decreased drastically with increasing glass fiber content. Laser ablation allowed us to observe process‐induced fiber orientation by scanning electron microscopy in PBT samples. For PS and PC, the weight loss increased with increasing injection flow rate and mold temperature and decreased with increasing injection pressure. The position near the gate showed higher ablation than the position at the end for all the conditions. A decrease in the material orientation with injection speed and mold temperature led to an increase in the weight loss, whereas an increase in the injection pressure, and consequently orientation, led to a lower weight loss for PS and PC. Higher residual stress samples showed higher weight losses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2006     

热氧老化对长玻璃纤维增强聚酰胺6复合材料的影响

研究了160℃条件下不同热氧老化时间对未添加抗氧剂和添加抗氧剂的长玻璃纤维(LGF)增强聚酰胺(PA)6(PA 6/LGF)复合材料力学性能、热稳定性、结晶度及表面形貌的影响,并采用热重分析,差示扫描量热法分析和扫描电子显微镜观察对PA 6/LGF复合材料进行了表征。结果表明:PA 6基体分子链的断裂、降解以及LGF与PA 6基体的脱黏导致了PA 6/LGF复合材料宏观力学性能、熔融温度、结晶温度、结晶度以及热稳定性的下降。添加抗氧剂的PA 6/LGF复合材料拉伸强度保持率为83.9%,而未添加抗氧剂的复合材料则为76.8%。添加抗氧剂能使PA 6/LGF复合材料具有相对优异的力学性能保持率。     

Preparation and characterization of high‐selectivity hollow fiber composite nanofiltration membrane by two‐way coating technique

A novel coating technique, named as two‐way coating (TWC), was explored to prepare hollow fiber composite (HFC) nanofiltration (NF) membrane through interfacial polymerization from piperazine (PIP) and trimesoyl chloride (TMC) on the lumen side of hollow fiber polysulfone ultrafiltration membrane with an effective membrane area of 0.4 m². The optimum preparation conditions were systematically investigated and obtained as follows: PIP 0.023 mol/L, TMC 0.0057 mol/L, air blowing rate 2.7 m/s for 30 min after aqueous coating, aqueous coating pressure 0.1 MPa, organic solution flowing rate 0.32 m/s, and heat treating time 3 min. The resultant HFC membrane showed a high selectivity of divalent ion and monovalent ion. Salt rejections of MgSO₄ and NaCl were 98.13 and 18.6% with the permeate flux of 32.6 and 40.2 L m^?2 h^?1 at 0.7 MPa, respectively. Field emission scanning electron microscopy images indicated that composite membrane prepared by TWC technique had a uniform active layer from the upper end to the bottom of the hollow fiber. And the salt rejection and permeate flux showed almost no difference between different membrane sections. Stability results suggested that good reproducibility could be obtained by TWC technique for the preparation of high‐performance HFC NF membrane. The resultant NF membrane showed a high removal rate of chemical oxygen demand and chroma of landfill leachate which were approximately 100%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41187.     

Performance and structure changes of the aromatic co‐polysulfonamide fibers during thermal‐oxidative aging process

The changes in performance during thermal‐oxidative aging process of the aromatic co‐polysulfonamide (co‐PSA) fibers over a broad temperature range from 250 °C to 320 °C have been investigated. In addition, the mechanism of thermal‐oxidative aging process has been studied by using structural information obtained from the fibers at varying length scales. The results showed that a significant reduction in tensile strength was observed compared with that of initial modulus during aging process. Macroscopically, thermal‐oxidative aging mainly causes color changes of fibers and thermally induced macro defects begin to appear only at 320 °C for 100 h. On a micro level, the crystal structure of fibers remained stable and did not show significant changes expect that aging at 320 °C. In addition, thermo‐degradation as well as crosslinking has been observed primarily in amorphous region. With the increase of temperature and time duration, the crosslinking became more dominant and crosslinking density increases. Correspondingly, the fibril length decreases due to degradation and then increases due to the formation of crosslinked structures within the fibers. The results suggest that molecular degradation is the main cause of strength loss and the formation of crosslinking structure within the fibers contributes to the retention of modulus and improvement of creep resistance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44078.     

Toughness optimization of elastomer‐modified glass–fiber reinforced PA6 materials

To investigate the influence of moisture and EPR‐g‐MA content on the fracture behavior of glass–fiber reinforced PA6 materials, brittle‐to‐tough transition temperatures (T_btt) were determined. Water absorption was taken into account by conditioning the analyzed materials. Tensile tests could reveal the temperature range of the largest moisture dependence of mechanical properties between 10 and 50°C. J‐integral values were used to describe the fracture behavior under conditions of impact load as a function of temperature. The brittle‐to‐tough transition of reinforced polyamides was found to be less approximate than in unreinforced materials. Two different characteristic temperature points T_s and T_e were identified, which were the intercept between elastic and elastic–plastic deformation on the one hand and the starting point of dominating stable crack propagation with strong plastic deformation on the other hand. Characteristic brittle‐to‐tough transition temperatures T_btt could be calculated as the arithmetic average of these two points. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of glass bead content and diameter on shrinkage and warpage of injection‐molded PA6

A simple technique has been introduced to evaluate the shrinkage and warpage behavior of injection molded products. Using the shrinkage values measured on specific locations of the specimen, three deformation factors have been defined to characterize the warpage behavior of the materials examined. Experiments were carried out to determine these properties of injection molded polyamide 6 (PA6) composites with solid glass bead (GB) contents of 10, 20, 30, 40 wt% and diameters of 11, 85, 156, 203 μm. It was concluded that the flow directional shrinkages can principally be described by the change in the bead content and diameter; it was proven that the increase in bead content and in bead diameter induces a reduction in flow directional shrinkage. The rising bead content and diameter increased the deformation factor, defined by the shrinkage differences caused by the pressure drop. It was pointed out that the ideal bead content can be determined in the function of bead diameter. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Preparation and characterization of graphene reinforced PA6 fiber

Here, we report the successful preparation of PA6/GO composite fibers through in situ polymerization and the melting spinning method. The results suggest that graphene has induced only minor changes on the relative viscosity yet exhibits significant effects on the crystallization characteristics. The SEM images of the fibers have shown several expended borders as a consequence of graphene addition. The maximum strength of the composite fibers (5.3 cN/dtex) has been reached 0.05 wt % graphene added to the system; the draw ratio was equaled to 3.8. Compared to the neat PA6 fiber, the fibers with graphene displayed superior creep resistance features; the creep rate constant was 0.38 at a 0.05 graphene concentration, with a draw ratio of 3.5. The approach employed in this research paves the way towards PA6/graphene nanocomposites have been prepared through in situ polymerization using caprolactam and graphene oxide/water pulp as starting materials. In situ polymerization approach facilitated a superior interaction between PA6 and graphene. Compared to graphene oxide powder, the graphene oxide in water pulp has prevented the agglomeration when added to the caprolactam melt, leading to its enhanced dispersion within the system. PA6/graphene as‐spun fiber has been produced by the mean of melt‐spinning strategy using a melt‐spinning machine, obtaining products with different draw ratios after drawing at 120 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45834.     

Melamine polyphosphate/silicon‐modified phenolic resin flame retardant glass fiber reinforced polyamide‐6

The halogen‐free flame retardance of glass fiber reinforced polyamide‐6 (PA6) is an everlastingly challenge due to well‐known wick effect. In this research, a novel system composed of a nitrogen–phosphorous flame retardant, melamine polyphosphate combined with a macromolecular charring agent, silicon‐modified phenolic resin (SPR), was employed to flame‐retard glass fiber reinforced PA6. It exhibited obvious synergistic effect between the two components at a proper ratio range. The flame retardance of the composites can be remarkably improved due to the increased amount and improved thermal stability of the produced char. The flame resistance tests indicated that the synergism system with an optimized ratio achieved V0 (1.6 mm) rating of UL94, 25.2% of Limited Oxygen Index, and only 338.2 W/g of the heat release peak rate. The corresponding synergistic mechanisms were investigated by the characterizations including the thermal gravimetric analysis, carbonation test, and the char morphology observation. It confirmed that the introduced SPR could accelerate the carbonation of PA6 resin, which was in favor of the construction of denser and more continuous charring structure. In addition, the flame retardant materials also indicated the acceptable mechanical properties, showing the advantages in the overall performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fundamental influences on quasistatic and cyclic material behavior of short glass fiber reinforced polyamide illustrated on microscopic scale

In this work, the influences of fiber orientation and weld lines on the morphological structures and the mechanical behavior of polyamide 6.6 (PA6.6‐GF35) are investigated. In quasistatic and fatigue tests tensile and 3‐point‐bending loads are applied. Test temperatures vary between RT and 150°C. Two different specimen types are produced by using injection moulding process to create different fiber orientations as well as weld lines. Fiber orientations are determined using computer tomography. Scanning electron microscopy is used to investigate fracture surfaces of tested specimens. Results show that mechanical properties and morphological structures depend highly on fiber orientation and temperature. Transversely oriented fibers in weld lines result in brittle failure mechanisms and decreased mechanical properties. Different stress distributions in the specimens under tensile and flexural loads have influence on the material behavior as well. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40842.     

Structure and property changes of polyamide 6 during the gel‐spinning process

Polyamide 6 (PA6) gels were prepared by the dissolution of PA6 powder in formic acid with CaCl₂ as a complexing agent. The concentration of the polymer was 16% w/v. PA6 fibers were obtained through gel‐spinning, drawing, decomplexation, and heat‐setting processes. The structure and properties of the fibers at different stages were characterized with differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The experiment results indicate that the melting transition of the as‐spun fibers obtained by the extrusion of the PA6/CaCl₂/HCOOH solution into a coagulation bath through a die disappeared. A porous structure existed in the as‐spun fibers, which led to poor mechanical properties. Compared with the as‐spun fibers, the melting and glass‐transition temperatures of the decomplexed and drawn fibers retained their original values from PA6, the degree of crystallinity increased, the porous structure disappeared, and the mechanical properties were improved. The maximum modulus and tensile strength obtained from the drawn fibers in this study were 32.3 GPa and 530.5 MPa, respectively, at the maximum draw ratio of 10. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4449–4456, 2013     

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     

Fatigue performance of injection‐molded short e‐glass fiber reinforced polyamide‐6,6. II. Effects of melt temperature and hold pressure

Tensile and fatigue properties of an injection molded short E‐glass fiber reinforced polyamide‐6,6 have been studied as a function of two key injection molding parameters, namely melt temperature and hold pressure. It was observed that tensile and fatigue strengths of specimens normal to the flow direction were lower than that in the flow direction, indicating inherent anisotropy caused by injection molding. Tensile and fatigue strengths of specimens with weld line were significantly lower than that without weld lines. For specimens in the flow direction, normal to the flow direction and with weld line, tensile strength and fatigue strength increased with increasing melt temperature as well as increasing hold pressure. The effect of specimen orientation on the tensile and fatigue strengths is explained in terms of the difference in fiber orientation and skin‐core morphology of the specimens. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers.     

短玻璃纤维增强低熔点尼龙6复合材料的性能研究

研究了短玻璃纤维用量对低熔点尼龙6(LMPA6)复合材料力学性能和热性能的影响。结果表明:随着短玻璃纤维用量的增加,LMPA6的缺口冲击强度先增加后降低,最高值为6.46KJ/m2;拉伸强度和弯曲强度则随之提高,当短玻璃纤维的用量为30%时,拉伸强度提高到100MPa,弯曲强度提高到130MPa以上。LMPA6的维卡软化点也随短玻璃纤维用量的增加而提高,当短玻璃纤维的用量为30%时,维卡软化点提高到90℃。     

Structure−property relationships of halogen‐free flame‐retarded poly(butylene terephthalate) and glass fiber reinforced PBT

Flame retardancy for thermoplastics is a challenging task where chemists and engineers work together to find solutions to improve the burning behavior without strongly influencing other key properties of the material. In this work, the halogen‐free additives aluminum diethylphosphinate (AlPi‐Et) and a mixture of aluminum phosphinate (AlPi) and resorcinol‐bis(di‐2,6‐xylyl phosphate) (AlPi‐H + RXP) are employed in neat and reinforced poly(butylene terephthalate) (PBT), and the morphology, mechanical performance, rheological behavior, and flammability of these materials are compared. Both additives show submicron dimensions but differ in terms of particle and agglomerate sizes und shapes. The overall mechanical performance of the PBT flame‐retarded with AlPi‐Et is lower than that with AlPi‐H‐RXP, due to the presence of larger agglomerates. Moreover, the flow behavior of the AlPi‐Et/PBT materials is dramatically changed as the larger rod‐like primary particles build a percolation threshold. In terms of flammability, both additives perform similar in the UL 94 test and under forced‐flaming combustion. Nevertheless, AlPi‐Et performs better than AlPi‐H + RXP in the LOI test. The concentration required to achieve acceptable flame retardancy ranges above 15 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Reducing water sorption of injection‐molded polyamide 6 bars by polymerization‐induced diffusion of styrene and grafting with polystyrene

An innovative method for reducing water sorption of injection‐molded polyamide 6 (PA6) bars by polymerization‐induced diffusion of styrene and grafting with polystyrene (PS) is reported. The process involves diffusion of styrene into PA6 bar in aqueous medium, addition of benzoyl peroxide to initiate polymerization of styrene, and further diffusion of styrene into the bar during polymerization. A hydrophobic PS‐rich shell consisting mainly of PS‐g‐PA6 can be formed in the surface layer of the PA6 bar, and as a result, the water sorption and dimensional change of PS‐modified PA6 bars reduce significantly. An incorporation of only 1.2% PS is sufficient, showing the advantage of this method over conventional melt mixing. The tensile modulus and strength of 1.2% PS‐modified PA6 bar increase slightly compared to those of neat PA6 bar due to reinforcement effect of rigid PS and reduced level of water‐caused plasticization, while maintaining the good ductility. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46243.     

Investigation of fiber orientation states in injection‐compression molded short‐fiber‐reinforced thermoplastics

Injection‐compression molding (ICM) has received increased attention because of its advantages over conventional injection molding (CIM). This article aims to investigate the effects of five dominating ICM processing parameters on fiber orientation in short‐fiber‐reinforced polypropylene (SFR‐PP) parts. A five‐layer structure of fiber orientation is found across the thickness under most conditions in ICM parts. This is quite different from the fiber orientation patterns in CIM parts. The fibers orient orderly along the flow direction in the shell region, whereas most fibers arrange randomly in the skin and the core regions. Additionally, the fiber orientation changes in the width direction, with most fibers arranging orderly along the flow direction at positions near the mold cavity wall. The results also show that the compression force, compression distance, and compression speed play important roles in determining the fiber states. Thicker shell regions, in which most fibers orient remarkably along the flow direction, can be obtained under larger compression force or compression speed. Moreover, the delay time has an obvious effect on the fiber orientation at positions far from the gate. However, the effect of compression time is found to be negligible. POLYM. COMPOS., 31:1899–1908, 2010. © 2010 Society of Plastics Engineers.     

Effects of mixing protocol on morphology and properties of PA6/ABS blends compatibilized with MMA‐MA

The effect of different mixing protocols in the preparation of PA6/ABS/MMA‐MA (57.5/37.5/5 wt %) blends on their morphological, rheological, thermal, thermomechanical, and mechanical behavior were studied. Despite the second‐phase size reduction due to copolymer incorporation, mixing sequence seems to play an important role in the properties of the blends. When PA6 is blended with the pre‐blended ABS/MMA‐MA system, compatibilizer is preferentially located in ABS phase and a co‐continuous structure is formed. The co‐continuity is believed to be responsible for the enhancements in toughness, but excessive presence of MMA‐MA in ABS phase seems to hamper thermomechanical properties. On the other hand, when ABS is blended with the PA6/MMA‐MA system previously prepared, compatibilizer is preferentially located in PA6 phase and a particle‐in‐matrix morphology is observed. The absence of excessive amount of MMA‐MA in ABS phase avoids the negative effect on thermomechanical resistance, however enhancements in toughness are not so pronounced. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43612.