SMA、OMMT对PA6/ABS共混物聚集态结构及性能影响的研究

采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)等手段研究了苯乙烯-马来酸酐共聚物(SMA)、有机蒙脱土(OMMT)对尼龙6(PA6)/丙烯腈-丁二烯-苯乙烯(ABS)共混物体系聚集态结构及性能的影响.结果表明,SMA与OMMT的加入均可提高PA6/ABS共混物体系的强度及模量,但加入OMMT后共混物的韧性有所下降,而PA6/ABS/SMA共混物的韧性随SMA含量的增加呈上升趋势.SMA、OMMT对PA6/ABS共混体系都有细化ABS分散相的作用,随SMA加入量的增加,ABS分散相尺寸逐渐减小,分布趋于均匀;当OMMT加入量在4 phr以内时,对ABS分散相粒径影响不大,超过4 phr后,随着OMMT含量的增加,ABS分散相的尺寸逐渐减小.XRD与TEM的分析结果表明,对PA6/OMMT(100/5)共混物,OMMT主要以剥离形态分布,同时也存在少量OMMT聚集体;PA6/ABS/OMMT共混物中OMMT则基本以剥离形态选择分布在PA6基体相中.     

PP/PP-g-MAH/PA6共混物结构与可纺性研究

运用DSC、SEM、纺丝成形等手段研究了增容剂聚丙烯接枝马来酸酐 (PP g MAH)对聚丙烯 聚酰胺 6(PP PA6 )共混物结构和性能的影响 .结果表明 ,共混物呈典型海岛型两相结构 ;增容剂PP g MAH与PA6之间的在位反应改善了PP PA6共混体系的相容性 ,使共混物中PA6的热结晶峰消失 ,PP的结晶生长速率和成核速率降低 ,可纺性提高     

端羟基聚丁二烯/增塑剂共混物相容性的分子动力学模拟和介观模拟

应用分子动力学(MD)和介观动力学(MesoDyn)模拟方法对固体推进剂中端羟基聚丁二烯(HTPB)与增塑剂癸二酸二辛酯(DOS)、硝化甘油(NG)的相容性进行了研究. 采用MD模拟方法在COMPASS力场下, 对纯物质、HTPB/增塑剂共混物的密度、内聚能密度、溶度参数和共混物分子间的Flory-Huggins作用参数及结合能等进行了模拟计算, 通过比较溶度参数差值(Δδ)的大小、模拟前后体系密度变化情况均可以预测HTPB与增塑剂的相容性, 结合能的分析揭示了HTPB/增塑剂共混物组分间的相互作用及本质. 将Flory-Huggins作用参数转化为MesoDyn模拟的输入参数, 采用MesoDyn模拟方法对HTPB/增塑剂共混体系的介观形貌与动力学演变过程进行了研究, 通过模拟得到的等密度图、自由能密度和有序度参数等可以判断共混体系的相容性. MD和MesoDyn模拟结果均表明: HTPB/DOS属于相容体系, 而HTPB/NG属于不相容体系, 其结论与实验结果一致.     

马来酸酐接枝热塑性弹性体在PP/PA6共混物中的作用

研究了马来酸酐接枝热塑性弹性体 (TPEg )作为增容剂对聚丙烯 (PP) 尼龙 6 (PA6 )共混体系的相容性、相态以及物理力学性能的影响 .研究结果表明TPEg的加入大大改善了PP PA6共混体系的相容性 ,且随TPEg含量的增大分散相粒径明显降低 ,共混物的韧性以及延展性大大提高 ,同时拉伸强度及模量仍保持较好的水平 .TPEg增容的PP PA6共混物的非等温结晶行为的研究表明 ,共混物中PP和PA6的结晶行为不同于各自纯的聚合物 ,PA6作为成核剂使PP的结晶温度提高 ;而PA6由于TPEg的加入 ,出现分级结晶现象 ,一级结晶温度略低于纯PA6的结晶温度 ,且随TPEg含量增大结晶受阻 ,二级结晶温度与PP的接近 .由于PP、PA 6以及TPEg之间存在较强的相互作用 ,三元共混物中PP及PA6的玻璃化转变温度分别较其纯聚合物升高 .基于上述结果 ,提出了本共混体系的结构模型     

PA6/HIPS/PP-g-(GMA-co-St)反应共混体系的研究

通过扫描电镜、热分析、熔体流动速率、熔融扭矩和力学性能等测试方法研究了甲基丙烯酸缩水甘油酯(GMA)和苯乙烯(St)多单体熔融接枝聚丙烯[PP-g-(GMA-co-St)]对PA6/HIPS共混物的熔融流变性能、结晶行为、相形态和力学性能的影响.结果表明,在熔融共混过程中,PP-g-(GMA-co-St)中的环氧基与PA6的端氨基原位生成的接枝共聚物有效地降低了共混物的界面张力,提高了共混物的界面粘着力,使共聚物的流动速率降低,熔融扭矩提高;PA6分子链的规整性降低,结晶完善性变差.在PP-g-(GMA-co-St)的质量分数为10%时,共混物分散相的尺寸明显减少,力学性能得到较大提高;其中冲击强度超过纯PA6,达到HIPS水平.通过反应共混,制备了力学性能均衡的PA6/HIPS/PP-g-(GMA-co-St)共混物合金.     

PP-g-(GMA-co-St)对PA6/PC共混物的反应增容作用

用红外、扫描电镜、熔体流动速率和力学性能等测试方法,研究了甲基丙烯酸缩水甘油酯(GMA)和苯乙烯(St)多单体熔融接枝聚丙烯[PP-g-(GMA-co-St)]对PA6/PC共混物的反应增容作用.研究结果表明,在熔融共混过程中,PP-g-(GMA-co-St)中的环氧基与PA6的端氨基及PC的端羟基原位生成的接枝共聚物有效地降低了共混物相间的界面张力,明显提高了共混物相界面的粘着力.少量的PP-g-(GMA-co-St)就能使PA6和PC的相容性得到显著改善.当PP-g-(GMA-co-St)的质量分数为10%时,共混物分散相的相区尺寸细化到0.2μm,其力学性能也有较大提高.PA6/PC/PP-g-(GMA-co-St)共混物的力学性能均衡,达到了弹性体增韧体系难以达到的效果.即使PP-g-(GMA-co-St)组分含量为20%时,共混物仍能保持较好的力学性能,特别是在共混物的韧性得以提高的同时,其强度和伸长率也提高.     

制备方法对聚合物共混物相分离与黏弹弛豫的影响

采用小角激光光散射(SALLS)和动态流变方法研究了通过不同制备方法得到的等规聚丙烯/乙丙橡胶共混物(iPP/EPR)的相分离行为与黏弹行为.依据Cahn-Hilliard-Cook理论分析了熔融共混和溶液共混法制备的质量比为60/40和40/60的iPP/EPR共混物在恒温相分离早期的动力学,发现熔融共混iPP/EPR具有更大的表观扩散系数(Dapp).相分离中后期的实验结果表明,当相区尺寸增长程度相同时,熔融共混试样所用时间更短.表明熔融共混iPP/EPR试样具有更快的相分离速率.动态流变测试结果表明,与溶液共混相比,熔融共混试样具有更快的松弛速率.考虑到相分离过程实质是由高分子链的运动与扩散所控制,两种方法制备的iPP/EPR共混物相分离速率的差异应归于其分子链运动能力的不同.     

氧化石墨烯增容尼龙6/聚苯乙烯共混体系的研究

氧化石墨烯(GO)亲水性的边缘和疏水性的中间片层使其具有两亲特性.利用GO的这种特性,将其加入尼龙6(PA6)/聚苯乙烯(PS)的共混体系,以提高PA6和PS的相容性.通过两步法制备了PA6/PS/GO共混物,研究了GO对PA6/PS共混材料结构形态与力学性能的影响,并对其增容机理进行了探讨.扫描电镜(SEM)结果表明,添加GO后,共混材料的分散相尺寸明显变小,分散更为均匀,少量的GO即可达到良好的增容效果.动态力学性能(DMA)测试进一步证明了GO对PA6/PS共混物具有一定的增容性.理论计算也表明PS/GO共混物和PA6具有更接近的表面自由能和较低的界面自由能.添加GO后共混物材料的拉伸性能和韧性明显提高.GO添加量为0.1 wt％时,共混材料的断裂伸长率较未添加GO的共混材料提高了170％,断裂能也提高了近240％.     

炭黑填充聚丙烯/尼龙6/玻璃纤维复合材料的制备及表征

以聚丙烯(PP)和尼龙6(PA6)的共混物为基体材料,以导电炭黑(CB)和玻璃纤维(GF)作为填料,通过熔融共混的方法制备了导电复合材料。研究了GF和CB质量分数对复合材料热稳定性、导电性能、力学性能和微观形貌的影响。结果表明:CB粒子选择性分散在PA6中,同时PA6包覆在GF表面,通过具有较大长径比的纤维相互搭接形成连续的网络结构,从而显著降低复合材料的逾渗阈值。在相同CB质量分数下(2%),PP/PA6/GF/CB的表面电阻率相对于PP/PA6/CB体系降低了5个数量级。此外,引入GF后,材料的热稳定性和拉伸强度都有所提高。     

γ-射线辐照法制备HDPE/PA6阻隔性材料及其性能研究

研究了富氧气氛中高密度聚乙烯(HDPE)的γ-射线辐照氧化及其与尼龙-6(PA6)的共混增容和共混材料的阻隔性能.FT-IR测试结果表明, 经γ-射线辐照的HDPE与PA6发生了化学反应或产生了弱相互作用.SEM照片显示4γHDPE (4h辐照,66Gy/min)与PA6具有良好的相容性,PA6在共混体系中呈层状分布.共混材料的阻隔性能测试结果表明4γHDPE/PA6共混物对二甲苯的阻隔性较HDPE/PA6共混物有明显提高.力学性能测试显示4γHDPE/PA6共混物力学性能优良.     

聚苯硫醚/尼龙6共混物界面对结晶行为的影响

高分子作为材料时 ,其力学性能受其结晶形态的影响 ,而其结晶形态与其结晶行为有关 .结晶性聚合物共混物中结晶组分由于第二组分存在 ,改变了结晶组分在熔体时的化学与物理环境 .因此 ,其结晶组分的结晶行为不仅取决于两组分在熔体时的相容性 ,而且与第二组分是否起到异相晶核作用和 /或两组分间界面是否诱导成核作用有关 ,从而影响共混物中结晶组分的结晶行为 ,导致共混物力学性能的改变[1～ 4] .在ＰＰＳ/ＰＡ6共混物中 ,由于ＰＰＳ的熔点和熔体结晶温度都比ＰＡ6的高 ,共混物熔体降温结晶ＰＰＳ是在ＰＡ6熔体存在下发生结晶 ,而ＰＡ6是在…     

RHEOLOGICAL BEHAVIOR OF POLYPHENYLENE SULFIDE/POLYAMIDE-66 BLENDS

Blends of polyphenylene sulfide (PPS) containing trace amounts of branching and/orcross-linking in chain and Polyamide-66(PA-66) have been prepared by melt blending. Therheological behavior of PPS/PA-66 blends has been studied by means of capillary rheo-meter, and compared with PPS. The effects of shear rate, shear stress and temperature onthe flow of PPS/PA-66 blends and PPS are discussed. The non-Newtonian indexes andthe activation energies of viscous flow are obtained. The results show that the apparentviscosity of PPS/PA-66 blends is not sensitive to shear rate and stress, but decreases withthe elevation of temperature. On the contrary, the apparent viscosity of the PPS decreasesobviously with the increasing of shear rate and shear stress, but it is increased by theelevation of temperatue.     

HDPE/PA6反应增容体系的形态演化与黏弹行为

采用扫描电子显微镜(SEM)与先进流变扩展系统(ARES),研究了马来酸酐接枝高密度聚乙烯(HDPE-g-MAH)对高密度聚乙烯/尼龙6(HDPE/PA6)共混体系形态结构和黏弹行为的影响.发现HDPE-g-MAH的加入可原位生成尼龙6-高密度聚乙烯接枝共聚物(HDPE-g-PA6),使基体与分散相间的相容性显著改善,且随其添加量的增加两者相容性更好,导致HDPE/PA6体系形态结构变化.研究结果表明,由ARES获得的体系黏弹行为参数随HDPE-g-MAH含量的变化可与由SEM所观察到的微观形貌演化很好关联,动态流变学方法可敏感表征增容剂的加入所引起的HDPE/PA6界面性质变化,且能够反映分子链间相互作用的变化及由此导致的分散相颗粒网络的形成.     

Largely enhanced ductility of immiscible high density polyethylene/polyamide 6 blends via nano‐bridge effect of functionalized multiwalled carbon nanotubes

Immiscible polymer blends usually exhibit negative deviation in mechanical properties compared with the corresponding pure polymers due to the weak interfacial bonding between the two polymers. Due to the bridge effect of the oriented carbon nanotubes (CNTs) on the craze and crack development at the load of stress, CNTs have been proved to be efficient toughening agent for polymers. In this work, functionalized multiwalled carbon nanotubes (FMWCNTs) have been introduced into immiscible high density polyethylene/polyamide 6 (HDPE/PA6) blends through different sample preparation methods. The mechanical measurements demonstrate that, when the nanocomposite is prepared from the HDPE master batch, the sample exhibits excellent tensile strength and toughness simultaneously. For all the nanocomposites, FMWCNTs tend to migrate and/or maintain in PA6 particles, leading to the variation of the crystallization behavior in PA6 phase. Further results based on morphologies characterization indicate that the intensified interfacial adhesion between HDPE and PA6, which is realized by the nano‐bridge effect of FMWCNTs in the interfaces, is the main reason for the largely improved ductility. Copyright © 2010 John Wiley & Sons, Ltd.     

ABS的MAH/St多单体熔融接枝及其对PA6/ABS共混体系相形态和力学性能的影响

通过多单体熔融接枝的方法制备出了具有较高接枝率的ABS接枝物 (ABS g (MAH co St) ) ,并对其接枝机理进行了初步探讨 .研究表明 ,MAH、St接枝ABS时 ,反应主要发生在ABS中聚丁二烯的双键部位 .同时 ,当MAH与St的用量比约为 1:1时接枝率达到最高 .ABS g (MAH co St)作为尼龙 6 (PA6 ) ABS共混体系相容剂起到了良好的增容效果 .实验证明 ,相容剂使用前后 ,共混物的相区尺寸由几十 μm减小到 1μm以下 ,且分布更加均匀 ;共混物的拉伸强度和冲击强度等力学性能也同时得到均衡改善 .     

聚苯硫醚及其聚砜共混物的结晶形态研究

应用偏光显微镜、扫描电子显微镜及蚀刻的方法,研究了聚苯硫醚及其与聚砜共混物的结晶形态与织构。结果表明,经固相空气热处理的聚苯硫醚,其本体与表面区域的结晶形态有显著的不同;蚀刻择优发生于球晶的晶界上;随着聚砜组份的增加,共混物的织构从聚苯硫醚为连续相逐渐转变为聚砜为连续相,聚苯硫醚的球晶形态也逐渐变得不规整。     

Influence of Reactive Compatibilization on the Melt Flow Properties and Morphology of Polyamide 6/Styrene-Acrylonitrile Blends

Summary: In this study, we investigate the influence of reactive compatibilization on the rheological properties of polyamide 6/styrene-acrylonitrile (PA 6/SAN) blends in the melt. Linear viscoelastic shear oscillations, simple elongation to a large stretch ratio and subsequent recovery experiments were performed. The morphology of the blends was examined by atomic force microscopy. We prepared three PA 6/SAN blends with different composition ratios of PA 6 and SAN (70/30, 50/50, 30/70) and a constant concentration of the reactive agent. Our experiments revealed that reactive compatibilization significantly increases the complex modulus of PA 6/SAN blends at low frequencies. In particular, the data of the PA 6/SAN 50/50 blend and the PA 6/SAN 30/70 blend indicated that an elastic network between neighbouring PA 6 domains was formed. In simple elongation, the transient elongational viscosity of the blends exceeded the values of the single components. In recovery, the recovered stretch of all blends was larger than the recovered stretch of the pure components. The differences of the blend morphology and of the linear viscoelastic behaviour were qualitatively explained by the asymmetric properties of the reactively compatibilized interface.     

Crystallinity and rheology of HDPE/PA12 blends compatibilized with HDPE-alt-MAH

This work studies the crystallinity and rheology of HDPE/PA12 blends compatibilized with 2 wt% of HDPE-alt-MAH. Specimens of HDPE/PA12 blends were extruded and injected into a mold with 75/25, 50/50, and 25/75 HDPE/PA ratios. The Fourier-transform infrared spectroscopy (FTIR) analysis showed that no oxidation reaction occurred in the high-temperature processing and that stronger interactions between the components of the blends occurred in the polyamide's functional groups. The x-ray diffraction (XRD) analysis showed that the crystallinity degree of the blends and the mean crystallite sizes decreased with the addition of PA12 for both blends. The HDPE's lattice parameters were consistent with the values in the literature, whereas for the PA12, it was not possible to fit its lattice parameters. The rheology analysis evaluated the relationship between the shear stress and viscosity and found that the HDPE/PA 75/25 blend was the most pseudoplastic, presenting the best processability under high shear rates.     

Effect of maleic anhydride-grafted ethylene-propylene rubber on the mechanical, rheological and morphological properties of organoclay reinforced polyamide 6/polypropylene nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic modified montmorillonite (organoclay) were compatibilized with maleic anhydride-grafted ethylene-propylene rubber (EPRgMA). The blends were melt compounded in twin screw extruder followed by injection molding. The mechanical properties of PA6/PP nanocomposites were studied by tensile and flexural tests. The microstructure of the nanocomposite were assessed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The dynamic mechanical properties of the PA6/PP blend-based nanocomposites were analyzed by using a dynamic mechanical thermal analyzer (DMTA). The rheological properties were conducted from plate/plate rheometry via dynamic frequency sweep scans. The melt viscosity in a high shear rate region was performed by using a capillary rheometer. The strength and stiffness of the PA6/PP-based nanocomposites were improved significantly with the incorporation of EPRgMA. Adding EPRgMA to the PA6/PP blends resulted in a finer dispersion of the PP phase. TEM and XRD results revealed that the organoclay was dispersed more homogeneously in the presence of EPRgMA, however, mostly in the PA6 phase of the blends. DMTA results showed that EPRgMA worked as an effective compatibilizer. The storage (G′) and loss moduli (G″) assessed by plate/plate rheometry of PA6/PP blends increased with the incorporation of EPRgMA and organoclay. Furthermore, the apparent shear viscosity of the PA6/PP blend increased significantly for the EPRgMA compatibilized PA6/PP/organoclay nanocomposite. This was traced to the formation of an interphase between PA6 and PP (via PA6-g-EPR) and effective intercalation/exfoliation of the organoclay.     

Morphology and mechanical properties of immiscible polyethylene/polyamide12 blends prepared by high shear processing

In this work,completely immiscible polyethylene/polyamidel2 (PE/PA12) blends were prepared by high shear extruder.The morphology and mechanical properties of the blends were investigated as a function of rotation speed.It wasfound that the high shear processing is an effective method to improve the dispersion of the PAl2 phase in PE matrix whenPAl2 contents are 5 wt％ and 10 wt％,and the dispersed phase particle size is reduced with the increase of rotation speed from 100 r/min to 500 r/min.However,with further increase of PAl2 content to 20 wt％,high shear processing has no effect on the phase morphology of the blends.Accordingly,a largely increased elongation at break and impact strength are observed for PE/PA12/95/5 and PE/PA12/90/10 blends obtained at high rotation speeds but no effect on the property of PE/PA12/80/20.Annealing experiment demonstrated that the obtained phase morphology is not stable thus compatibilizer should be introduced in the future work.This work could provide a guideline for the application of high shear processing in the preparation of polymer blends with huge polarity difference.