Influence of thermooxidative aging on the static and dynamic mechanical properties of long‐glass‐fiber‐reinforced polyamide 6 composites

The static and dynamic mechanical properties, thermal behaviors, and morphology of pure long‐glass‐fiber‐reinforced samples [polyamide 6 (PA6)/long glass fiber (LGF)] with different thermal exposure times at 160°C were studied by comparison with stabilized samples in this study. The aging mechanism of the PA6/LGF samples under heat and oxygen was studied with the methods of thermal Fourier transform infrared (FTIR), differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy (SEM), and so on. The results indicate that the static mechanical strength, melting temperature, and crystallization temperature decreased because of the decomposition of the macromolecular chain of PA6 resin and the debonding of the interface between the glass fibers and matrix. The glass‐transition temperature and crystallinity also increased and decreased, respectively, after aging. The macromolecular chain decomposition dominated in the subsequent aging process; this resulted in many sharp and brittle microcracks appearing on the surfaces of the aged samples, as shown by SEM and the FTIR spectra. The existence of stabilizers endowed the PA6/LGF composites with better retention of static and dynamic mechanical properties. The reason was that the metal ions of the copper salt antioxidant acted as an anti‐aging catalyst in the reinforced PA6 system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39594.     

Stress photo‐oxidative aging behaviour of polyamide 6

The long‐term stress accelerating aging behaviour of polyamide 6 (PA6) was studied by exposure to UV irradiation. The aging behaviour and mechanism were investigated in terms of creep behaviour, mechanical properties, chemical structure, crystallization and orientation behaviour. It was found that the creep deformation of PA6 under stress/UV irradiation was lower than that of the sample aging only under stress, resulting from crosslinking and low mobility of molecules under UV irradiation. The tensile strength of PA6 under stress and stress/UV irradiation substantially increased at the primary aging stage due to stress‐induced molecular orientation. The oxidation of PA6 may also be inhibited by orientation, leading to a relatively low content of carboxylic groups. Under UV irradiation, stress accelerates the degradation of PA6, resulting in strengthening UV absorption due to formation of isolated carbonyl groups. The melt temperature and crystallinity both showed an increase with time, which were much higher for the sample aged under stress/UV irradiation than for that aged only under UV irradiation. Wide‐angle X‐ray diffraction analysis also showed that the orientation factor and crystallinity of PA6 increased with aging time before 16 days, indicating a clear orientation and crystallization of molecules induced by stress. The UV‐induced crosslinking reduced the mobility of PA6 chains, resulting in a lower crystallinity and orientation factor of the sample aged under stress/UV irradiation compared with that under stress aging only. Copyright © 2011 Society of Chemical Industry     

Thermal aging of a blend of high‐performance fibers

The focus of this work is the study of the thermal aging of high‐performance fibers used in the making of fire protective garments. Accelerated thermal aging tests were carried out on fabric samples made up of a blend of Kevlar® (poly p‐phenylene terephthalamide) and PBI (poly benzimidazole) staple fibers, as well as on yarns pulled from this fabric, by means of exposure to elevated temperatures, comprised between 190°C and 320°C. All samples underwent loss of breaking force retention. The material thermal life, defined as the time required for the fibers to attain a 50% reduction of the original breaking force, ranged between a dozen of days at the lowest exposure temperature, to less than an hour at the highest. Breaking force data were fitted using the Arrhenius model following two different approaches, namely the extrapolated thermal life value and the shift factors yielded by the time‐temperature superposition (TTS). The Arrhenius model seemed to describe appropriately the overall aging process, as inferred from the excellent fit obtained when using both approaches, although activation energies provided from both approaches are different. To follow the chemical evolution of the material with thermal aging, Fourier‐transform infrared (FTIR) analyses were conducted. The qualitative analysis of the FTIR spectra showed little evidence of chemical changes between the aged and the nonaged samples, indicating either that the aging process carries on without significant modification of the chemical structure of the fibers, or that FTIR is not an appropriate method to spot such a modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Stress–thermooxidative aging behavior of polyamide 6

The long‐term stress–thermooxidative aging behavior of polyamide 6 (PA6) was studied in terms of the creep behavior, mechanical properties, chemical structure, crystallization, and orientation behavior. During aging, a thermooxidation reaction occurred, which included molecular chain degradation and crosslinking, in PA6. Meanwhile, when the samples were subjected to stress, crystallization, orientation, and chain scission were induced. In the initial stages of aging, the stress‐induced crystallization and orientation dominated; this resulted in an increase in the creep deformation, mechanical strength, crystallinity, and orientation factor. Molecular degradation and chain scission dominated in the subsequent aging process and resulted in a decrease of the mechanical strength, reduced viscosity, crystallinity, and orientation factor and an increase in the formation of oxide and peroxide products. The stress may have promoted the chain scission of PA6 during thermal aging and resulted in a decrease in the reduced viscosity and an increase in the carboxylic acid concentration. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

几种帘子线的热收缩性能的研究

分析了聚酰胺6、聚酰胺66、聚酯帘子线的物理-机械性能，研究了各种帘子线的热收缩与温度预张力之间的相关性。结果表明：帘子线的热收缩率随温度的升高而增大，随预张力的增加而减小。热收缩应力随温度升高而增加。     

应变状态下徐冷玻璃态PVC老化现象研究

通过机械拉伸试验和差示扫描量热法(DSC)等手段对物理老化和应变老化的聚氯乙烯(PVC)试样进行研究。力学性能测试结果表明:应变状态下老化试样的屈服应力和弹性模量均大于物理老化试样的屈服应力和弹性模量,而断裂伸长率则相反。这说明PVC试样在应变状态下的老化导致材料脆性增加。DSC测试中,观察到应变状态下老化试样的吸热峰随着时间的增加表现在滞后于物理老化试样。这种现象可以解释为应变状态下老化试样形成了与物理老化试样不同的结构。     

Characterization of alkali‐treated jute fibers for physical and mechanical properties

Changes occurring in jute fibers when treated with a 5% concentration of a NaOH solution for 0, 2, 4, 6, and 8 h were characterized by weight loss, linear density, tenacity, modulus, FTIR, and X‐ray measurements. A 9.63% weight loss was measured during 2 h of treatment with a drop of hemicellulose content from 22 to 12.90%. The linear density value showed no change until 2 h of treatment followed by a decrease from 33.0 to 14.5 denier by 56% after 6 h of treatment. The tenacity and modulus of the fibers improved by 45 and 79%, respectively, and the percent breaking strain was reduced by 23% after 8 h of treatment. X‐ray diffractograms showed increase in crystallinity of the fibers only after 6 h of treatment, while FTIR measurements showed much of the changes occurring by 2 h of treatment with an increased amount of OH groups. By measuring the rate of change of the modulus, tenacity, and percent breaking strain with the time of treatment, a clear transition was apparent at 4 h of treatment with the dissolution of hemicellulose, causing a weight loss and drop in the linear density before and development of crystallinity with an improvement in the properties after the transition time. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1013–1020, 2001     

Effect of ethylene–acrylate–(maleic anhydride) terpolymer on mechanical properties and morphology of poly(ethylene terephthalate)/polyamide‐6 blends

Background: Poly(ethylene terephthalate) (PET)/polyamide‐6 (PA‐6) blends are promising for engineering and food‐packaging applications. However, their poor toughness limits their use. In this study, an ethylene–acrylate–(maleic anhydride) terpolymer (E‐AE‐MA) was added to PET/PA‐6 blends in order to improve the toughness. Results: Izod impact tests indicated an excellent toughening effect of E‐AE‐MA. E‐AE‐MA particles were observed to be selectively dispersed at the interface between PET and PA‐6 phases and in the domain of the PA‐6 phase. Fourier transform infrared spectroscopy and differential scanning calorimetry results demonstrated that the formation of E‐AE‐MA layers around PA‐6 particles cut off the interaction between PET and PA‐6, resulting in an enlarged PA‐6 phase domain. Conclusion: Based on the experimental results, a core–shell microstructure, with PA‐6 as a hard core and E‐AE‐MA as a soft shell, could be suggested. The formation of this core–shell microstructure, along with the increased PA‐6 phase domain size, is the main toughening mechanism of E‐AE‐MA in PET/PA‐6 blends. Copyright © 2007 Society of Chemical Industry     

Mechanical,Thermal, and Morphological Behavior of Silicone Rubber during Accelerated Aging

An accelerated aging study on silicone rubber exploring the effects of exposure to a functional oil (polyalkylene glycol) at elevated temperature (195°C) is reported in this paper. Variations in mechanical (tensile, tear, hardness) and thermal (conductivity, specific heat capacity) properties were monitored versus aging time while permanent deformation of the rubber was evaluated through creep and recovery measurements. Morphology and surface chemistry of the aged rubber were also investigated through scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy, respectively. Aging had a significant impact on the mechanical properties with the ultimate tensile strength and elongation at break decreasing from 7.4?MPa and 2250% in unaged samples to 1.5?MPa and 760% in 6-week aged samples, respectively. The tear strength and hardness exhibited an initial increase during the early stages of aging, followed by a decreasing trend. In contrast, the thermal properties did not change significantly and FTIR did not detect any changes in the surface chemistry of the rubber with aging. SEM however, provided evidence of an increase in brittle behavior from the morphology of the fractured surfaces.     

Morphology and Crystallization of Biobased Polyamide 56 Blended with Polyethylene Terephthalate

This study attempts to promote biobased polyamide 56 (PA56) as a sustainable candidate to replace commercial PA6 and PA66 when blended with polyethylene terephthalate (PET). Scanning and transmission electron microscopy of the blends with different PA56 contents reveals an immiscible morphology with an increase in the size of the dispersed domains by increasing PA56 content. The steady‐state mixing torque of the kneader is decreased to half by adding 10 wt% of PA56 to PET. Further addition of PA56 gradually increases this torque but does not surpass the neat PET sample up to 30 wt% of PA56. As revealed by microscopic dissipative particle dynamics (DPD) simulations, this gradual increase is ascribed to the difficulty to disperse larger domains of PA56 in the thermodynamically undesired PET. The results confirm that PA56 has a lubricating effect in PET. Using polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD) techniques, it is shown that PA56 acts as a nucleating agent in PET. This leads to the formation of numerous small crystals in the blends as opposed to several large crystals in the neat samples. The results encourage the use of PA56 biomaterial in combination with PET in products such as bicomponent segmented pie fibers.     

Water absorption and hygrothermal aging study on organomontmorillonite reinforced polyamide 6/polypropylene nanocomposites

The water absorption and hygrothermal aging behavior of organomontmorillonite (OMMT) reinforced polyamide 6/polypropylene (PA6/PP ratio = 70/30), with and without maleated PP (MAH‐g‐PP), was studied at three different temperatures (30, 60, and 90°C). The water absorption and hygrothermal aging response of the composites was studied and analyzed by tensile tests and morphology assessment (scanning electron microscopy and transmission electron microscopy), indicating the effect of the immersion temperature, OMMT, and MAH‐g‐PP compatibilizer. The mathematical treatment used in analyzing the data was the single free phase model of diffusion, which assumed Fickian diffusion and utilized Fick's second law of diffusion. The kinetics of water absorption of the PA6/PP nanocomposites conformed to Fickian law behavior, whereby the initial moisture absorption follows a linear relationship between the percentage gain at any time t and t^1/2 (the square root of time), followed by saturation. It was found that the equilibrium moisture content and the diffusion coefficient are dependent on the OMMT loading, MAH‐g‐PP concentration, and immersion temperatures. Both the tensile modulus and strength of the PA6/PP nanocomposites deteriorated after being exposed to hygrothermal aging. MAH‐g‐PP acted as a good compatibilizer for PA6/PP/OMMT nanocomposites, which was attributed to its higher retention ability in modulus and strength (in the wet and redried states), lower equilibrium moisture content, and reduced water diffusivity of the nanocomposites. Morphological sketches for both uncompatibilized and MAH‐g‐PP compatibilized PA6/PP/OMMT nanocomposites, toward water uptake are proposed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 780–790, 2005     

X‐ray diffraction,Raman, and differential thermal analyses of the thermal aging of a Kevlar®‐PBI blend fabric

A previous study of the effects of thermal aging on the tensile properties of a fabric made of a 60–40 wt % blend of Kevlar and PBI fibers has shown that exposure to elevated temperatures between 190 and 320°C results in a rapid decrease in tensile breaking force retention. In this article, X‐ray diffraction and Raman spectroscopy analyses were carried out to evaluate the consequences of thermal aging on the material's crystallinity. Differential thermal analyses were also undertaken to examine the evolution of the glass transition temperature of PBI following thermal exposure. X‐ray diffraction profiles show a gradual increase in the crystallinity with temperature and aging time, whereas a complete disappearance of spectral lines for aged samples in Raman analysis suggests instead a decrease in crystallinity as a consequence of exposure to elevated temperatures. The seemingly contradictory outcome obtained when using the two techniques led to the proposal of a new, alternative hypothesis to explain the observed results. This hypothesis involves two simultaneous events that occur during thermal aging: the increase of crystallite size in the direction parallel to coplanar sheets, and the disruption of the crystalline lattice in the direction perpendicular to those sheets. The glass transition temperature of PBI was found to shift towards the lower temperatures after thermal aging, a phenomenon that can be associated with random polymer chain scission caused by thermal aging. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

PTT/PA6拉伸丝的形态与性能的研究

考察了聚对苯二甲酸丙二醇酯/聚酰胺6(PTT/PA6)拉伸丝的形态,测试了其线密度、断裂强度、回潮率、热收缩率及卷曲性能,并与聚对苯二甲酸乙二醇酯/聚酰胺6(PET/PA6)拉伸丝进行了对比.结果表明:PTT/PA6拉伸丝横截面为橘瓣型,裂离后为三角形.PTT/PA6拉伸丝的断裂强度、断裂功和卷曲收缩率随纺丝速度的增加...     

Rheological,thermal and morphological properties of polyethylene terephthalate/polyamide 6/rice husk ash composites

This work deals with the rheological, morphological, and thermal properties of composites having poly(ethylene terephthalate) (PET), polyamide-6 (PA6), and their blends as matrices, and rice husk ash (RHA) as a filler. The study determines the effect of composition on the change in viscosity and rate of degradation during processing in a torque rheometer. Our data indicates that thermal stability and degradation during processing depend on matrix composition and filler concentration. SEM micrographs show both partial adhesion of the filler to the matrices and filler pullout. Optical microscopy shows particle agglomeration and that agglomerate size increased with filler content. FTIR investigates the shifting of absorption bands of PET/PA6 composite after the addition of RHA and attributes the selective dispersion of RHA to the formation of hydrogen bonds. Our data supports the idea that filler employed here is an option to develop polymer composites with improved properties.     

Lifetime prediction of carboxyl-terminated polybutadiene (CTPB)

Carboxyl-terminated polybutadiene (CTPB) was subjected to temperature and humidity aging in order to estimate its useful lifetime as a solid propellant binder. CTPB samples were temperature aged from 1 week to 7 months at various temperatures ranging from 50 to 100°C. At various stages of temperature aging, viscosity of the samples were measured, end group analyses were performed, and the samples, after being crosslinked with MAPO, were mechanically tested. As far as mechanical properties are concerned, the ultimate tensile stress of the samples decreases with temperature aging and strain at break increases. End group analyses indicate that acid value of the samples decreases with aging and viscosity increases. The results of temperature aging were applied to an Arrhenius type time-temperature superposition relation and useful lifetime of CTPB as binder at 20°C was predicted to be around 10 years. The CTPB samples were also humidity-aged and the effects of humidity aging on mechanical properties were investigated. The results indicate that similar to temperature aging, ultimate tensile strength decreases and strain at break increases with aging. The effects of humidity aging, however, is much less pronounced in comparison to temperature aging.     

In situ fibrillar reinforced PET/PA‐6/PA‐66 blend

Ternary fibrillar reinforced blends are obtained by melt‐blending of poly(ethylene terephthalate) (PET), polyamide 6 (PA‐6) and polyamide 66 (PA‐66) (20/60/20 by weight) in the presence of a catalyst, followed by cold drawing of the extruded bristles to a draw ratio of about 3.4 and additional annealing of the drawn blend at 220 or 240°C for 4 or 8 h. The blend samples are studied by DSC, X‐ray diffraction, SEM, and static and dynamic mechanical testing (DMA). SEM and DMA show that PA‐6 and PA‐66 form a homogeneous, continuous matrix in which PET regions are dispersed. X‐ray and DSC measurements of the drawn and annealed at 220°C samples suggest mixed crystallization (solid solubility) of PA‐6 and PA‐66, and cooperative crystallization of PET with the two polyamides. After annealing at 240°C (above the melting point of PA‐6 and below that of PET), the polyamide matrix becomes partially disoriented, while the oriented, fibrillar PET is preserved and plays the role of a reinforcing element. The DSC results for the same samples suggest in situ generation of an additional amount of copolymer. This additional copolymerization, together with that generated during blend mixing in the extruder, improves the compatibility of the blend components (mostly at the PET‐polyamide interface) and alters the chemical composition of the blend.     

熔体直纺涤锦复合超细纤维产品研发

探讨聚酯熔体直纺涤锦米字型复合POY超细纤维工艺技术,研究表明:在纺制涤锦复合POY超细纤维规格为290 dtex/72 f时,涤锦2组份质量比PET:PA6为82:18,PET熔体温度为285～290℃,PA6纺丝温度为(270～274)℃,纺丝速度(3000～3300)m/min,冷却风温为(20～22)℃,冷却风...     

玻璃纤维增强聚酰胺老化机理的研究

以30％玻纤增强的聚酰胺66（PA66）为对象，用紫外加速仪研究了辐照时间对玻纤增强PA66的吸湿率、力学性能和形貌的影响进行研究，探讨了玻纤增强PA66的老化机理。实验结果表明：玻纤增强聚酰胺经紫外老化后的吸湿率显著低于未增强聚酰胺；玻纤增强聚酰胺的拉伸强度、弯曲强度显著提高，紫外老化后力学性能保持率较高；玻纤增强聚酰胺抗老化的机理可能是玻璃纤维阻止了聚酰胺老化裂纹的进一步扩展，同时减缓了外界因素对聚酰胺本体的进一步侵蚀，老化速度减慢。     

Coloring effect of the organic hybrid of polyamide 6 and N,N′‐ethylene‐bis(tetrabromophthalimide)

Coloring study in organic hybrid of polyamide (PA6) and N,N′‐ethylene‐bis(tetrabromophthalimide) (EPT), where the chromophore was self‐assembled by hydrogen bonding formed between PA6 molecular chains and EPT compound, have been characterized by several techniques. CS930 double wavelength lamella scanner was employed to measure the change of color. The existence of hydrogen bonding in PA6/N‐N′‐ethylene‐bis (tetrabromophthalimide) (PA6EPT) was investigated with Fourier transform infrared (FTIR), the results of which were compared with that of PA6 with the same thermal history. FTIR spectra at room temperature revealed that there is essentially hydrogen bonding between PA6 and EPT. The crystallization behavior of PA6EPT affected by hydrogen bonding was studied by using FTIR. The temperature‐dependent behavior of both PA6 and PA6EPT was studied by temperature‐FTIR spectroscopy and differential scanning calorimetry (DSC). With temperature increasing, changes in sensitive, high‐resolution absorbance spectra are observed as dissolve‐volatilizing thin film. Temperature‐FTIR results showed that the hydrogen bonding in PA6EPT attenuated and dissociated considerably at a smaller rate than PA6, that is to say, hydrogen bonding in PA6EPT is more stable than that in PA6. DSC showed that the melting temperature of PA6EPT and PA6 are similar. However, the crystalline degree and crystalline temperature and melting enthalpy of PA6 and PA6EPT are different. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 594–600, 2007     

Flame retardancy of glass fiber reinforced high temperature polyamide by use of aluminum diethylphosphinate: thermal and thermo‐oxidative effects

Glass fiber reinforced polyamide (PA) 6 T/DT flame retarded with aluminum diethylphosphinate (AlPi) was tested to assess its flame retardant properties. Models for the decomposition of PA 6T/DT with and without AlPi are presented. Thermal decomposition was measured by performing TGA with Fourier transform infrared (FTIR) spectroscopy and FTIR spectroscopy in the condensed phase. Fire behavior was studied using a cone calorimeter and flammability was tested with UL 94 and the limiting oxygen index. AlPi works as an effective flame retardant for glass fiber reinforced PA 6T/DT materials, acting in the gas phase. Also observed was condensed‐phase action, which occurs especially under oxidative conditions before the samples ignite. © 2013 Society of Chemical Industry