β晶相聚丙烯纺丝工艺的研究

本文研究了三种不同β晶成核剂的聚丙烯切片的纺丝工艺条件与初生纤维中结晶结构的关系。研究表明,制得的初生纤维中的β晶含量主要取决于含β成核剂聚丙烯的结晶速率和纺丝成形中的冷却速率。含β成核剂E3B聚丙烯的结晶速率最大,纺制的初生纤维β晶含量最高;纺丝成形中的冷却速率愈高,初生纤维中的β晶含量愈低;在一定的温度范围内,纺丝温度对初生纤维中β晶相对含量影响甚微;纺丝冷却条件和纤维束的集束状况对β晶含量有明显的影响;β晶的晶粒尺寸与β晶含量相对应,而初生纤维中的结晶度多在55％左右,受纺丝工艺参数的影响甚小。     

力场下聚合物的结晶行为研究进展

介绍了聚合物在力场作用下结晶行为的研究进展;概述了不同力场(剪切、拉伸、振动)对聚合物结晶形态和结晶动力学的影响;重点论述了剪切力场下,剪切速率、剪切方式、分子量和分子量分布等对聚合物成核和生长的影响,简述了拉伸、振动对结晶的影响。认为力场的加入对聚合物的成核和晶体生长都有促进作用。     

冷却速率对β成核剂改性PP结晶行为的影响

利用差示扫描量热仪研究了冷却速率对β成核剂改性聚丙烯(PP)结晶行为的影响。冷却速率越慢,高温停留时间越长,则PP中β晶型含量越高,PP的冲击强度越高。冷却速率为5℃/min时,PP中β晶型质量分数达86.12%;冷却速率为20℃/min时,β晶型质量分数为72.04%;而当试样以极快速冷却时,β晶型含量为0。β晶型PP的结晶速率慢于α晶型PP,只有在较高的温度范围内等温结晶时,β晶型PP的结晶速率才快于α晶型PP。因此,一般加工工艺条件下β晶型含量较少。     

尼龙成核剂的研究与进展

尼龙材料在工程塑料、纤维材料中占有重要的地位,且随着近年来合成长链尼龙单体生产的实现,其应用更受关注。尼龙材料的性能与材料的聚集态结构中结晶结构密切相关。成核剂是一种用于改变结晶型聚合物的结晶度和结晶形态,加快结晶速率并改善聚合物性能的加工助剂。常用的尼龙成核剂可以分为无机成核剂、有机成核剂、复合成核剂三类。该文以聚合物结晶理论和成核剂作用机理为基础,介绍不同种类成核剂的加入对尼龙的晶型、结晶速率、结晶度、拉伸强度、弯曲性能、冲击强度以及透明度等结构与性能上的影响。     

不同的β成核剂聚丙烯的结晶性能研究

本文报导了用偏光显微镜观察IPP切片中β球晶的生长过程和形态;借助DSC法、光学解偏振法和大角X衍射法研究含不同β成核剂的IPP在等温和非等温条件下的结晶能力。实验结果表明,对比三种不同的成核剂,发现其结晶速率为RPP>DC>GD,而在纺丝过程中由于成核速率占主导作用,因此卷绕丝中β晶含量也为RPP>DC>GD。研究结果还表明,提高结晶温度,降低冷却速率,有利于提高β晶聚丙烯中的β晶含量。     

山梨糖醇/稀土复合成核剂对等规聚丙烯非等温结晶行为的影响

采用差示扫描量热仪(DSC)研究了山梨糖醇/稀土复合成核剂不同组成对等规聚丙烯非等温结晶动力学及其熔融行为的影响。动力学分析结果表明莫志深方法很好地描述聚丙烯非等温结晶动力学,用Kissinger公式计算所得非等温结晶活化能表明复合成核剂的加入提高了结晶活化能。结晶形态和熔融行为均依赖于复合成核剂的组成和降温冷却速率,较低的降温速率有利于β晶型的生成,随着降温速率的增加,β晶型的相对含量减少。在较多的β成核剂含量和较低的降温速率条件下,可以获得较高含量的β晶型。     

碳纤维增强聚酰胺6复合材料的结晶行为研究

通过偏光显微镜和差示扫描量热仪(DSC)研究了碳纤维(CF)和滑石粉对聚酰胺6(PA6)结晶行为的影响。结果表明,CF的加入在PA6和CF的界面诱发横晶,CF和滑石粉在PA6基体中起到了异相成核作用,改变PA6的成核机理和晶体生长方式,提高了起始结晶温度和结晶速率。结晶速率随普等温结晶温度的升高而下降。当冷却速率增大时,起始结晶温度下降,结晶度增大。     

酰胺类β成核剂对PP R非等温结晶动力学影响

研究了酰胺类β晶型成核剂对无规共聚聚丙烯(PP R)非等温结晶动力学的影响。结果表明,β成核剂提高了PP R的结晶峰温。在相同的冷却速率下,β成核剂改性PP R体系的Zc比纯PP R小,半结晶时间t1/2比纯PP R长;达到相同结晶度时,β成核剂改性PP R体系所需的冷却速率大于纯PP R,这说明β成核剂的加入降低了PP R的结晶速率。莫法可以很好地表征PP R及β成核剂改性PP R体系的非等温结晶行为。     

聚丙烯复合材料的非等温结晶动力学

采用差示扫描量热仪研究了β成核剂和水滑石(LDH)/β成核剂复配的成核剂对聚丙烯(PP)非等温结晶动力学及熔融行为的影响。结果表明:加入成核剂后,PP中晶体分布不均匀且分散度增大。莫志深方法采用F(θ)表征聚合物在单位时间内达到某一结晶度时所需的冷却(或加热)速率,结晶度达到40%时,纯PP的F(θ)为3.82,加入β成核剂的PP的F(θ)为3.30,加入LDH/β成核剂的PP的F(θ)为2.49。与纯β成核剂相比,LDH/β成核剂能更好地提高PP的结晶温度、结晶速率,增强PP的β晶熔融峰,减弱β晶和α晶共存熔融峰和α晶熔融峰。     

UHMWPP／UHMWPE合金纤维非等温结晶动力学研究

运用DSC手段研究了UHMWPP／UHMWPE合金纤维的等温结晶行为，对所得的实验数据用修正Avrami方程的Jeziorny法进行处理，发现随冷却速率的提高，半结晶的时间t1/2缩短，表明冷却速率加快时，结晶速率也随之加快，纯UHMWPP主要是以三维球晶的方式进行结晶生长，UHMWPE的加入起到核剂的作用，随着成核剂含量的增加，UHMWPP的结晶维数将降低.     

Crystallization kinetics and nucleating agents for enhancing the crystallization of poly(p-phenylene sulfide)

An experimental study of crystallization kinetics and the influence of nucleating agents on the solidification of poly(p-phenylene sulfide) (PPS) is described. The effect of molecular weight is considered by investigating PPS samples having different viscosity levels. We studied the effect of a range of nucleating agents including aluminum oxide, calcium oxide, silicon dioxide, titanium dioxide, kaolin, and talc. All of these compounds were found to enhance the rate of crystallization; in particular, silicon dioxide, kaolin, and talc were the most effective nucleating agents. An effort to study particle size effects of the silicon dioxide showed that the nucleation was very sensitive to the source of the material. These studies did, however, show that nucleation rates tended to increase with decreasing particle size and increasing loading of silicon dioxide. Comparison of PPS crystallization rates with those of other polymers indicates that it crystallizes much more slowly than polyethylene or isotactic polypropylene and is slower than polyetherether-ketone, when comparisons are made on an equivalent basis. PPS crystallizes at similar rates to polyethylene terephthalate (PET). However, our nucleated PPS does not crystallize as rapidly as nucleated PET.     

纳米SiO2粒子对PET结晶过程的影响

研究了纳米SiO2粒子对PET结晶过程的影响。通过差热分析(DSC),分别研究了改性纳米SiO2对PET的等温结晶和非等温结晶的影响。计算了在不同温度下,不同改性纳米SiO2含量PET的等温结晶动力学方程。结果表明:随着纳米SiO2的加入,可以显著提高PET的结晶性能,Avrami指数n变小,体系发生异相成核。当纳米SiO2的添加量在2％时,体系的结晶能力最好,在所测的5个等温结晶温度中,所有样品在170℃附近的结晶速度最快。     

Crystallization of oriented isotactic polypropylene (iPP) in the presence of in situ poly(ethylene terephthalate) (PET) microfibrils

The present article reports the nonisothermal crystallization process and morphological evolution of oriented iPP melt with and without in situ poly(ethylene terephthalate) (PET) microfibrils. The bars of neat iPP and PET/iPP microfibrillar blend were fabricated by shear controlled orientation injection molding (SCORIM), which exhibit the oriented crystalline structure (shish-kebab), especially in the skin layer. The skin layer was annealed at just above its melting temperature (175 °C) for a relatively short duration (5 min) to preserve a certain level of oriented iPP molecules. It was found that the existence of ordered clusters (i.e. oriented iPP molecular aggregates) leads to the primary nucleation at higher onset crystallization temperature, and formation of the fibril-like crystalline morphology. However, the overall crystallization rate decreases as a result that the relatively high crystallization temperature restrains the secondary nucleation. With the existence of PET microfibrils, the heterogeneous nucleation distinctly occurs in the unoriented iPP melt and results in the increase of crystallization peak temperature and overall crystallization rate, for the first time, we observed that the onset crystallization temperature has been enhanced further with addition of PET microfibrils in the oriented iPP melt, indicating the synergistic effect of row nucleation and heterogeneous nucleation under quiescent condition.     

Non-isothermal crystallization kinetics of TiO2 nanoparticle-filled poly(ethylene terephthalate) with structural and chemical properties

The present research work includes non-isothermal crystallization kinetics of poly(ethylene terephthalate) (PET)–titanium dioxide (TiO₂) nanocomposites as well as structural and chemical properties of these nanocomposites. The average grain size of chemically synthesized TiO₂ nanoparticles has been calculated 19.31 nm by TEM and XRD. The morphology and structural analysis of PET–TiO₂ nanocomposites, prepared via solution casting method, has been investigated using SEM and XRD, respectively. The nature of chemical bonds has been discussed on the basis of FTIR spectra. The effect of TiO₂ nanoparticles and cooling rates on non-isothermal crystallization kinetics of PET was examined by differential scanning calorimetry at various heating and cooling rates. It has been observed that TiO₂ nanoparticles accelerate the heterogeneous nucleation in PET matrix. The crystallization kinetics could be explained through Avrami–Ozawa combined theory. TiO₂ nanoparticles cause to make molecular chains of PET easier to crystallize and accelerate the crystallization rates during non-isothermal crystallization process; this conclusion has also been verified by Kissinger model for crystallization activation energy.     

纳米氧化物作为成核剂对PET结晶速率的影响

研究了成核剂纳米氧化镁和纳米氧化硅对聚对苯二甲酸乙二醇酯(PET)结晶速率的影响。通过等温结晶差热分析(DSC)研究了纳米氧化镁在不同含量、不同温度下对PET等温结晶行为的影响。用纳米氧化镁和纳米氧化硅填充PET体系的非等温结晶DSC,由所得冷结晶峰温度值和热结晶峰温度值的对比,探索纳米成核剂对PET结晶速率的影响及其规律。研究结果表明:纳米成核剂均能明显提高PET的结晶速率,而纳米氧化镁比纳米氧化硅对促进PET的结晶效果更好;添加不同含量的纳米氧化镁对PET在不同温度下的等温结晶影响不同,在所研究的范围内,1.0%的添加量较有利于PET的结晶。     

Effect of rod-like imide unit on crystallization of copoly(ethylene terephthalate-imide)

The effect of the imide unit on the isothermal and non-isothermal crystallization, kinetics crystallization of a new family of copoly(ethylene terephthalate-imides) (called copolyesterimides or PETIs) was investigated using differential scanning calorimetry. With a combined Avrami and Ozawa equation, one can describe the non-isothermal crystallization process of copolyesterimides, and the results show the same tendency as that in the isothermal crystallization process. These studies show that the processes of crystal nucleation and growth result in mainly three-dimensional growth with a thermal nucleation. In both isothermal and non-isothermal crystallization processes, the crystallization rate of PETIs, with imide content below 0.5%, is higher than that of neat PET, while PETI-3 (0.3 mol% imide) has the highest crystallization rate. This rate is significantly enhanced over PET homopolymer. It is proposed that imide units precipitate from the melt and act as nucleating agents during the crystallization process of these novel copolyesterimides.     

Nonisothermal Crystallization and Melting Behaviors of PP/PA6/TiO2 Nanocomposites

Titanium dioxide nanoparticles were functionalized with toluene-2,4-diisocyanate and then polypropylene/polyamide 6 blends containing functionalized titanium dioxide were prepared using a twin-screw extruder. The nonisothermal crystallization and melting behaviors of the as-prepared nanocomposites were investigated using differential scanning calorimetry. The nonisothermal crystallization differential scanning calorimetry data were analyzed by the modified-Avrami (Jeziorny) and combination of Ozawa and Avrami (Mo) methods. It can be found that the Jeziorny method can be used to describe the main crystallization process, and the Mo method can better deal with nonisothermal crystallization kinetics of the polypropylene and polyamide 6 phase in polypropylene/polyamide 6-based nanocomposites. The nonisothermal crystallization analysis shows that the titanium dioxide nanoparticles have two effects on polypropylene/polyamide 6 blends, i.e., it can favor the improvement of crystallization ability and decrease the crystallization rate of the polypropylene and polyamide 6 phase in polypropylene/polyamide 6-based nanocomposites. For one thing, the functionalized titanium dioxide nanoparticles in the polypropylene/polyamide 6-based nanocomposites act as effective nucleation agents and result in higher crystallization temperature (T₀) than that of the polypropylene and polyamide 6 in pure polypropylene/polyamide 6 blends, which indicated titanium dioxide nanoparticles favor the improvement of crystallization ability of the polypropylene and polyamide 6 phase. For another, the existence of functionalized titanium dioxide nanoparticles hinders the free movement of polymer chains and results in lower crystallinity than that of the polypropylene and polyamide 6 in pure polypropylene/polyamide 6 blends, which indicated titanium dioxide nanoparticles decrease the crystallization rate of the polypropylene and polyamide 6 phase in polypropylene/polyamide 6-based nanocomposites. The nonisothermal crystallization melting behaviors show that there is single or double melting peak, which varies with different cooling rates for the polyamide 6 phase in polypropylene/polyamide 6-based nanocomposites. Multiple melting peak is mainly caused by the different crystalline structure of the polyamide 6 phase, the melting peak I is mainly caused by γ crystal of the polyamide 6 phase, while the melting peak II corresponds to the thermodynamic stability of α crystal. Besides, the recrystallization of the polyamide 6 phase in the heating process, and the effect of the incorporation of the titanium dioxide nanoparticles may have some contributions to the appeared multiple melting peak of the polyamide 6 phase in the polypropylene/polyamide 6-based nanocomposites.     

PTT的非等温结晶动力学研究

采用DSC方法对PTT在不同冷却速率下的结晶过程进行了研究,并与PET进行了对比,其结晶动力学用Mandel Kern方法来处理。结果表明,PTF相对于PET更易成核结晶,PTT半结晶时间比PET长,冷却速率对PTT的半结晶时间影响大,并且PTF的非等温结晶动力学曲线的线性较PET好,能够更好的遵循Mandel Kern方法。     

Nonisothermal crystallization kinetics and morphology of poly(ethylene terephthalate) modified with poly(lactic acid)

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) copolymers modified with poly(lactic acid) (PLA) were investigated with differential scanning calorimetry, and a crystal morphology of the samples was observed with scanning electron microscopy. Waste PET (P100) obtained from postconsumer water bottles was modified with a low‐molecular‐weight PLA. The PET/PLA weight ratio was 90/10 (P90) or 50/50 (P50) in the modified samples. The nonisothermal melt‐crystallization kinetics of the modified samples were compared with those of P100. The segmented block copolymer structure (PET‐b‐PLA‐b‐PET) of the modified samples formed by a transesterification reaction between the PLA and PET units in solution and the length of the aliphatic and aromatic blocks were found to have a great effect on the nucleation mechanism and overall crystallization rate. On the basis of the results of the crystallization kinetics determined by several models (Ozawa, Avrami, Jeziorny, and Liu–Mo) and morphological observations, the crystallization rate of the samples decreased in the order of P50 > P90 > P100, depending on the amount of PLA in the copolymer structure. However, the apparent crystallization activation energies of the samples decreased in the order of P90 > P100 > P50. It was concluded that the nucleation rate and mechanism were affected significantly by the incorporation of PLA into the copolymer structure and that these also had an effect on the overall crystallization energy barrier. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The nucleation, crystallization and dispersion behavior of PET-monodisperse SiO2 composites

To more accurately investigate the nucleation, crystallization and dispersion behaviors of silica particles in polymers, the composites of PET with monodisperse SiO₂-PS core-shell structured particles were prepared with SiO₂ size from 380 nm to 35 nm.For these SNPET samples, DSC results showed that the nucleation rate of silica particles increased as their size decreased, in which 35 nm SiO₂ particles produced the most obvious nucleation effect. At 2.0 wt.% load of 35 nm silica, Avrami equation proved that the isothermal crystallization rate G of SNPET was ca. 30% higher than that of pure PET and the crystallization activation energy for SNPET was −218.7 kJ mol⁻¹ lower than −196.1 kJ mol⁻¹ for PET. While, the non-isothermal crystallization ΔE for SNPET was −199.8 kJ mol⁻¹ lower than −185.5 for PET.On non-isothermal crystallization, Jeziorny equation presented the primary and secondary crystallization stages in PET and SNPET, in which nano SiO₂ accelerated the crystallization rate. Their Ozawa number m was from 2.1 to 2.7, which was smaller than that of Avrami number n.The nucleation and dispersion behaviors of SiO₂ particles were directly observed. POM results demonstrated that SNPET samples crystallized more quickly from melt and their crystallization rate increased as silica load increases but accelerated at 2-3 wt.%. The spherulites grew well in PET but their size was smaller in SNPET due to the silica barrier on their growth. SEM and TEM observed the homogeneous silica dispersion morphology and the vivid ordered patterns formed in SNPET. The monodisperse particles are highly expected to give more accurate and valuable references than multi-scale ones in obtaining novel advanced PET composites.