Morphology evolution, crystalline orientation, and thermal expansion of PA6/SEBS blends with nanolayer networks

A blend of polyamide 6 (PA6) and styrene-ethylene/butylene-styrene (SEBS) with a co-continuous nanolayer network was fabricated by reactive compounding and subsequent injection molding. The nanostructured polymer alloy was found to exhibit an extremely low coefficient of linear thermal expansion (CLTE) in the flow direction, accompanied by a largely suppressed molding shrinkage. To clarify the influence of the microstructure on thermal expansion behavior, a systematic study of morphology evolution, crystalline orientation, and confined crystallization of the PA6/SEBS (60/40) blend was carried out by means of TEM, DMA, DSC and WAXD measurements. It was found that a lower viscosity of SEBS and the capability of in situ compatibility with PA6 enable a morphology evolution from a disordered co-continuous to droplet-continuous and, finally, to a nanolayer network structure. Multi-scale orientations take place during the injection molding process, and the large reduction of CLTE may originate from the high order microstructure in two aspects: (1) the rubber-deformation-induced orientation of PA6 crystalline in which the b-axis with a negative CLTE orients along the flow direction, and (2) the co-continuous orientation of the rubber and plastic nanolayers, of which the thermal expansion favors towards the normal direction.     

The effects of SEBS-g-maleic anhydride reaction on the morphology and properties of polypropylene/PA6/SEBS ternary blends

Ternary blends, based on 70% by weight of polypropylene (PP) with 30% by weight of a dispersed phase, consisting of 15% polyamide-6 (PA6) and 15% of a mixture comprising varying ratios of an unreactive poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) triblock copolymer and a reactive maleic anhydride-grafted SEBS-g-MA, were produced via melt blending in a co-rotating twin-screw extruder. TEM revealed the blend containing only non-reactive SEBS to exhibit individual PA6 and SEBS dispersed phases. However, the progressive replacement of SEBS with reactive SEBS-g-MA increased the degree of interfacial reaction between the SEBS and PA6 phases, thus reducing interfacial tension and providing a driving force for encapsulation of the PA6 by the SEBS. Consequently, the dispersed-phase morphology was observed to transform from two separate phases to acorn-type composite particles, then to individual core-shell particles and finally to agglomerates of the core-shell particles. The resultant blends exhibited significant morphology-induced variations in both thermal and mechanical properties. DSC showed that blends in which the diameter of the PA6 particles was reduced to ≤3 μm by the increasing interfacial reaction exhibited fractionated PA6 crystallisation. In general, mechanical testing showed the blends to exhibit inferior low-strain tensile properties (modulus and yield stress) compared to the matrix PP, but superior ultimate tensile properties (stress and strain at break) and impact strength. These changes are discussed with reference to composite models.     

SEBS的臭氧处理及增韧PA6的研究

研究了臭氧处理对氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)分子结构及其极性的影响,并对臭氧处理SEBS增韧PA6进行了研究。结果表明,通过臭氧处理可在SEBS分子链上引入羰基含氧基团,臭氧处理的SEBS相对分子质量下降,相对分子质量分布变宽,表面能提高,极性增大。与PA6／SEBS体系相比,PA6／臭氧处理SEBS体系的相容性得到明显改善,其冲击强度和断裂伸长率大幅度提高。     

反应挤出PA6/SEBS原位合金的制备与表征

以己内酰胺和马来酸酐接枝氢化苯乙烯-丁二烯嵌段共聚物(SEBS-g-MA)为原料,通过反应挤出己内酰胺阴离子开环聚合法制备尼龙6(PA6)/氢化苯乙烯-丁二烯嵌段共聚弹性体(SEBS)原位合金。首先研究了SEBS-g-MA对己内酰胺阴离子开环聚合速率及单体转化率的影响,并对原位合金进行了红外光谱、扫描电镜以及力学性能测试。结果表明,合金制备过程中原位生成了SEBS-g-PA6增容物;随着SEBS-g-MA含量的增加,聚合速率延缓,单体含量略有增加;扫描电镜图像发现SEBS-g-PA6起到了很好的增容作用,原位合金的拉伸强度有所减小,断裂伸长率和缺口冲击强度分别是纯PA6的7倍和2.4倍。     

Effect of SEBS on morphology, thermal, and mechanical properties of PP/organoclay nanocomposites

A simultaneously increase in stiffness and toughness is needed for improving polypropylene (PP) competitiveness in automotive industry. The aim of this paper is to investigate the effects of styrene-(ethylene-co-butylene)-styrene triblock copolymer (SEBS) on mechanical and thermal properties of PP, in the presence and the absence of nanoclay. The amount of SEBS in PP was ranged to obtain the matrix with the most favorable stiffness–toughness balance. For this purpose, SEBS domain size and distribution in PP/SEBS blends was determined by means of atomic force microscopy and correlated with mechanical properties. The influence of SEBS on the crystalline structure of PP in PP/organoclay nanocomposites was investigated by X-ray diffraction and differential scanning calorimetry, a synergistic effect of SEBS and nanoclay being pointed out. Moreover large improvement in the impact strength (almost 22 times) was obtained in the case of SEBS-containing nanocomposite in comparison with the composite without SEBS.     

SEBS增韧PPO/PA6合金结构与性能研究

采用双螺杆熔融挤出的方法制备了氢化(苯乙烯-丁二烯-苯乙烯)共聚物(SEBS)增韧聚苯醚/聚酰胺6(PPO/PA6)合金。通过扫描电子显微镜(SEM)、差示扫描量热(DSC)分析、毛细管流变分析、动态热机械分析(DMA)等方法研究了PPO/PA6合金的断面形貌、结晶性能、流变性能和动态力学性能。结果表明:加入SEBS后,共混合金的断裂方式由脆性断裂向韧性断裂转变;合金材料的结晶度降低,表观黏度提高,储能模量下降,冲击性能得到明显改善。     

共混顺序对石墨烯微片在PP/PA6/SEBS共混物中的选择性分布和迁移的影响

研究了聚丙烯(PP)/聚酰胺6(PA6)/氢化苯乙烯-丁二烯嵌段共聚物(SEBS)/石墨烯微片(GNPs)纳米复合材料在不同共混顺序下的微观形貌、导电及导热性能,分析了GNPs在复合体系中的选择性分布和迁移及其对复合材料性能的影响.结果表明,在PP/PA6/SEBS/GNPs共混体系中,GNPs在界面张力的作用下趋向于...     

SEBS和SEBS-g-MAH对PPO/PA66合金性能影响的研究

在双螺杆挤出机上采用共混挤出的方法制备了苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)和马来酸酐接枝苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS-g-MAH)增韧的聚苯醚(PPO)/聚酰胺66(PA66)合金。通过力学性能测试、扫描电子显微镜观察和吸水性实验,研究了SEBS和SEBS-g-MAH及其含量对PPO/PA66合金性能的影响。结果表明,SEBS-g-MAH增韧PPO/PA66合金体系的力学性能较好,吸水率较小。     

GMA接枝SEBS及其对PA 6的改性及增容

用双螺杆反应挤出法将甲基丙烯酸缩水甘油酯(GMA)接枝到氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)上(即SEBS-g-GMA)，研究引发剂过氧化二异丙苯用量、活性单体GMA用量对接枝率的影响；通过双螺杆挤出、共混，制备聚酰胺(PA)6／SEBS-g-GMA、PA 6／SEBS-g-GMA／SEBS合金，研究SEBS-g-GMA对合金体系的相容性影响及增韧作用，探讨了合金体系的形态结构和力学性能。     

Mechanical properties and morphology of PA6/EVA blends

The mechanical properties of blends of polyamide6 (PA6) and ethylene vinyl acetate (EVA) at a blending composition of 0–50 wt % EVA were studied. The notched Izod impact strength of PA6 increased with the incorporation of EVA, the increase being more than 100% compared to PA6 at 10% EVA. The tensile strength and the tensile modulus of the blends decreased steadily as the weight percent of EVA increased. Analysis of the tensile data using predictive theories indicated the extent of the interaction of the dispersed phase and the matrix up to 20 wt % EVA. SEM studies of the cryogenically fractured surfaces indicated increase in the dispersed phase domain size with EVA concentrations. On the other hand, impact fractured surfaces of PA6/EVA blends indicated debonding of EVA particles, leaving hemispherical bumps, indicating inadequate interfacial adhesion between PA6 and EVA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1593–1606, 2002     

PA66/SEBS复合材料的制备与性能研究

以聚酰胺66(PA66)和苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)为原料,3份马来酸酐接枝苯乙烯-乙烯-丁二烯-苯乙烯共聚物(SEBS-g-MAH)为增容剂,通过熔融共混法制备了PA66/SEBS复合材料,研究了SEBS添加量对复合材料结晶性能、热性能、界面相容性、力学性能等的影响。结果表明:SEBS的加入没有改变PA66的特有晶型,仅仅改变了不同晶型的相对含量;随着SEBS用量的增加,PA66/SEBS复合材料的熔融温度、界面相容性下降,拉伸强度也呈逐渐降低的趋势;随着SEBS用量的增加,未加增容剂的复合材料的断裂伸长率呈逐渐减小的趋势,而加入增容剂的复合材料的断裂伸长率则呈先增后减的趋势;另外,加入了增容剂的复合材料的力学性能明显优于未加增容剂的复合材料。     

Effect of different size complex fillers on thermal conductivity of PA6 thermal composites

ABSTRACT

Nylon 6 (PA6) thermal conductive composites were prepared by melt blending with different sizes of spherical Al₂O₃ and AlN and the filling amount was 60 wt%. This paper explored the effects of different particle sizes and filler kinds on the thermal conductivity and mechanical properties of the composites. The results showed that the composites filled with AlN and spherical Al₂O₃ had higher thermal conductivity than the composites filled with single filler under the same filling amount. When the mass ratio of 48 μm spherical Al₂O₃ and 14 μm AlN was 1:2, the thermal conductivity and thermal diffusivity was 2.44 W/(m·K) and 0.72 mm²/s, respectively. In addition,the tensile strength was 57.50 MPa and the impact strength was 6.13 KJ/m². By comparing actual thermal conductivity value with the theoretical value calculated by Agari model, we found that actual value of alumina filling was close to the theoretical value.     

PA6/TLCPa的相容性、结晶性能及其形貌

采用挤出成型制备了聚酰胺(PA)6/热致聚酰胺液晶(TLCPa)原位复合材料,研究了共混物的相容性、结晶性能和形貌.结果表明:TLCPa和PA 6具有较好的相容性,并存在分子间氢键作用;TLCPa掺人到PA 6的结晶过程中降低了PA 6的结晶度;PA 6的球晶大小随w(TLCPa)的而增大,当w(TLCPa)为30.0...     

Structural,rheological, and mechanical properties of PA6/SAN/SEBS ternary blend/organoclay nanocomposites

The aim of this study was to investigate the effect of nanoclay addition on the morphological and mechanical properties of PA6/SAN/SEBS ternary blend. Two different nanoclays with different modifiers and two different mixing sequences were used to investigate the role of thermodynamic and kinetic, respectively, in the nanoclays localization. XRD, SEM, TEM, melt rheology, tensile and Izod impact tests were used to characterize the nanocomposites. Results of characterization of nanocomposites showed that clay localization is a very influential parameter to determine the type of morphology and, consequently, mechanical properties of ternary/clay nanocomposites. It was demonstrated that presence of nanoclay in the matrix results in the increase of stiffness, while localization of nanoclay at the interface improves the toughness and tensile strength. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41969.     

Mechanical,chemical, thermal,and rheological properties of recycled PA6/ABS binary and PA6/PA66/ABS ternary blends

The effects of multiple injection molding cycles on the chemical and mechanical properties of PA6/ABS and PA6/PA66/ABS blends are investigated. The chemical structures of both PA6/ABS binary and PA6/PA66/ABS ternary blends do not alter after recycling process. For PA6/ABS binary blend, it is found that the tensile strength, strain at break, elastic modulus, impact strength, flexural strength, and modulus of recycled blend decrease by 6.49%, 15.19%, 21.00%, 9.41%, 7.09%, and 8.25%, respectively, while MFI increases by 23.59% as compared with the virgin blend. After five recycling process for PA6/PA66/ABS ternary blend, the tensile strength, strain at break, and impact strength of recycled blend decrease by 18.00%, 50.80%, and 87.27%, respectively. However, flexural strength and modulus of PA6/PA66/ABS blend increase slightly. For virgin PA6/PA66/ABS blend, MFI value was 7.7 g/10 min and with recycling this value showed an important increase to 31.56 g/10 min after five cycles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40810.     

PA／PP／SEBS三元合金的结构与性能

本文作者采用氢化ＳＢＳ（ＳＥＢＳ）三嵌段热塑性弹性体增韧ＰＡ／ＰＰ共混体系，应用挤出反应技术在双螺杆挤出机内就地产生相容剂，可改善体系的相容性，从而获得了超高韧性的尼龙合金，还采用ＳＥＭ和ＴＥＭ技术研究了此类体系的形态结构特征，这些形态结构为进一步研究结构与性能关系提供了丰富的资料。     

相容剂对PVC／PA6体系形态结构的影响

研究了SMA—g—MAH、SEBS—g—MAH和EVA—g—MAH3种相容剂对PVC／PA6共混物的增容效果。结果表明,未添加相容剂的PVC／PA6（100／20）共混物的相容性不好;添加SEBS—g—MAH和EVA—g—MAH两种相容剂后,PVC／PA6共混物的相容性得到一定程度的改善;添加SMA—g—MAH相容剂后,PA6很均匀地分散在PVC基体中。     

Nanofiltration membranes based on PA6/EVOH with variable composition and morphology

Nanofiltration PA6/EVOH membranes were prepared through a nonsolvent induced phase separation technique. The effects of polymer concentration in the solution and solvent evaporation time on the performance and morphology of the resulting membranes were investigated by cloud point titration, permeation, and scanning electron microscopy (SEM). Experimental cloud point data for various prepared membranes suggested that polymer solutions with higher concentrations of PA6/EVOH need a less content of nonsolvent. SEM observations show that an increase in polymer concentration leads to formation of a thin dense layer on the surface of the membrane thanks to pore size reduction. However, dense top layer of membrane becomes thicker as polymer concentration increases from 15 wt% to 20 wt%. The performance of membranes reveals a decrease with polymer concentration in casting solution. By contrast, Polyamide/Poly(ethylene‐co‐vinyl alcohol) membranes show an optimal performance with various formic acid evaporation times. J. VINYL ADDIT. TECHNOL., 25:E28–E34, 2019. © 2018 Society of Plastics Engineers     

Effect of in situ synthesized macroactivator on morphology of PA6/PS blends via successive polymerization

In situ polymerization and in situ compatibilization was adopted for preparation of ternary PA6/PS‐g‐PA6/PS blends by means of successive polymerization of styrene, with TMI and ε‐caprolactam, via free radical copolymerization and anionic ring‐opening polymerization, respectively. Copolymer poly(St‐g‐TMI), the chain of which bears isocyanate (? NCO), acts as a macroactivator to initiate PA6 chain growth from the PS chain and graft copolymer of PS‐g‐PA6 and pure PA6 form, simultaneously. The effect of the macroactivator poly(St‐g‐TMI) on the phase morphology was investigated in detail, using scanning electron microscopy. In case of blends with higher content of PS‐g‐PA6 copolymer, copolymer nanoparticles coexisting with the PS formed the matrix, in which PA6 microspheres were dispersed evenly as minor phase. The content of the compositions (homopolystyrene, homopolyamide 6, and PS‐g‐PA6) of the blends were determined by selective solvent extraction technique. The mechanical properties of PA6/PS‐g‐PA6/PS blends were better than that of PA6/PS blends. Especially for the blends T10 with lower PS‐g‐PA6 copolymer content, both the flexural strength and flexural modulus showed significantly improving because of the improved interfacial adhesion between PS and PA6. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of clay addition on the morphology and thermal behavior of polyamide 6

The nanostructure, morphology, and thermal properties of polyamide 6 (PA6)/clay nanocomposites were studied with X‐ray scattering, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). The wide‐angle X‐ray diffraction (WAXD) and TEM results indicate that the nanoclay platelets were exfoliated throughout the PA6 matrix. The crystallization behavior of PA6 was significantly influenced by the addition of clay to the polymer matrix. A clay‐induced crystal transformation from the α phase to the γ phase for PA6 was confirmed by WAXD and DSC; that is, the formation of γ‐form crystals was strongly enhanced by the presence of clay. With various clay concentrations, the degree of crystallinity and crystalline morphology (e.g., spherulite size, lamellar thickness, and long period) of PA6 and the nanocomposites changed dramatically, as evidenced by TEM and small‐angle X‐ray scattering results. The thermal behavior of the nanocomposites was investigated with DSC and compared with that of neat PA6. The possible origins of a new clay‐induced endothermic peak at high temperature are discussed, and a model is proposed to explain the complex melting behavior of the PA6/clay nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1191–1199, 2007