聚丙烯熔体流动中结构化的流变学研究

<正> 各种流场对高分子流体流变性质的不同影响及其分子机理的探索是当今流变学中引入注目的课题。本文提供一个有兴趣的例子:聚丙烯熔体在入口收敛流中发生结构化,又在随后的毛细管切流动中消除。 全同立构聚丙烯在约210℃以下挤出会发生熔体流变性质和加工性质的特征性变化,一些作者不恰当地将流动曲线和粘度-温度关系的反常笼统归结为切力诱导结晶和熔化时剩余的有序结构,要弄清这一问题应进行更细致的实验,尤其应分析入口收敛流场和毛细管中剪切场起的不同作用。     

冷态模型系统模拟介质糖浆溶液粘弹性的分析

利用旋转流变仪和毛细管流变仪研究了不同葡萄糖浆溶液的粘弹性,结果表明:不同除水量的糖浆溶液的零剪切粘度(η0)呈现指数增长规律;不同PAM添加量对糖浆溶液的储能模量(G′)和损耗模量(G″)影响较大,且对G′的影响较为显著;随着PAM(聚丙烯酰胺)含量的增加,松弛时间和挤出胀大比(B)逐渐增大,糖浆溶液弹性越来越明显;其它条件相同,零剪切粘度越大,糖浆溶液的弹性效应越明显;糖浆溶液在20~80℃温度范围内粘度可逆,温度对糖浆溶液粘度的影响非常显著,且粘度变化相差可达1000倍。     

几种典型含氟树脂流变行为研究概述

主要对乙烯-四氟乙烯共聚物(ETFE)、聚全氟乙丙烯(FEP)、聚偏氟乙烯(PVDF)、全氟磺酸树脂(PFSA)和全氟羧酸树脂(PFCR)这几种典型含氟树脂的加工流变行为和线性粘弹性进行了综述。FEP高速挤出时稳定流动区非常窄,并且进行模型拟合时发现其剪切流动行为符合Carreau模型。ETFE为热流变简单高分子,其剪切粘度、拉伸粘度、挤出胀大和动态模量等流变函数均可进行时温叠加。在低剪切速率下,PVDF熔体表现出牛顿流体行为;在高剪切速率下,PVDF熔体呈现出剪切稀化现象。PFSA和PFCR熔体的表观黏度随剪切速率、温度的升高而降低,流动曲线显示该熔体属于假塑性流体。     

微孔中简单流体粘度的分子动力学模拟及关联模型

用分子动力学模拟计算了微孔介质中流体氩在不同温度、不同密度和不同孔径下的剪切粘度.并根据Chapman-Enskog关于硬球流体传递性质的理论以及Heyes的关于Lennard-Jones流体粘度的表达式,提出了两个描述微孔介质中流体粘度的模型,该模型可以计算微孔中流体氩在不同状态下的粘度值.通过与计算机模拟值的比较,证明这两个微孔流体粘度模型是可用的.     

超高分子量聚苯乙烯的流变性能

以毛细管流变仪和Hakke转矩流变仪对稀土催化合成的超高分子量聚苯乙烯 (UHMWPS)的流变与加工性能进行了研究 .结果表明 ,UHMWPS最显著的流变特征为超高的熔体粘度和低剪切速率下出现不稳定流动 .不稳定流动与超高分子量聚合物长的松弛时间有关 ,并提出了临界剪切速率与分子量和温度的定量关系式 .较低的分子量和较高的温度有利于提高临界剪切速率 ,改善挤出物外观质量和降低熔体粘度 .分子链极度缠结不仅导致超高的熔体粘度 ,也使UHMWPS链解缠加快 ,导致更高的剪切速率敏感性 .UHMWPS塑化时熔体粘度高 ,转矩大 ,加工性能劣于通用聚苯乙烯 (GPPS)     

新型聚芳醚酮与热致性液晶高聚物共混物流变性能和力学性能的研究

本文研究了新型聚芳醚酮与热致性液晶高聚物(PEK-C/LCP)共混物的流变性能及力学性能。结果表明:由于LCP的加入,PEK-C的熔体粘度降低;随着剪切速率的增加,共混物熔体流动活化能从223.5KJ/mol降为102.2KJ/mol。共混物的玻璃化转变温度从纯PEK-C的218℃降为199℃;除模量增加外,其它力学性能均有所下降。同时利用SEM观察了共混物冲击断面形貌,未发现有LCP微纤维生成。     

新型聚芳醚酮与热致性液晶高聚物共混物流变性能和力学性能的研究

 本文研究了新型聚芳醚酮与热致性液晶高聚物(PEK-C/LCP)共混物的流变性能及力学性能。结果表明:由于LCP的加入,PEK-C的熔体粘度降低;随着剪切速率的增加,共混物熔体流动活化能从223.5KJ/mol降为102.2KJ/mol。共混物的玻璃化转变温度从纯PEK-C的218℃降为199℃;除模量增加外,其它力学性能均有所下降。同时利用SEM观察了共混物冲击断面形貌,未发现有LCP微纤维生成。     

钇铝石榴石纤维纺丝原液的制备及结构与流变性研究

以铝粉、工业盐酸和醋酸钇为主要原料,水为溶剂,通过溶胶-凝胶法制备了钇铝石榴石(YAG)纤维前驱体纺丝原液。采用XRD表征了纺丝液热处理后的物相组成,采用²⁷Al核磁共振、FTIR和旋转流变仪分别研究了纺丝液的结构、红外吸收特性和流变学行为。结果表明,在900 ℃下热处理可以得到单一的钇铝石榴石晶相。通过²⁷Al核磁共振和红外吸收光谱的变化分析了YAG溶胶的形成机理,认为YAG溶胶是由体系内活性羟基的缩聚反应而生成的线性结构的胶体。YAG纺丝液的纺丝性依赖于其流变性和粘度,具有纺丝性能的胶体为剪切变稀的假塑性流体,粘度在2～4 Pa·s。研究了纺丝液的非牛顿指数与含水量的关系,纺丝性能最好的胶体的非牛顿指数为0.78。     

静电纺丝纤维直径的数学模型预测和实验验证

目前,静电纺丝纤维直径的预测数学模型有Fridrikh模型、Spivak模型和Stepanyan模型。前两种模型的两个主要参数是纺丝液的表面张力和射流的体积电荷密度,Stepanyan模型的两个主要参数是纺丝液的零剪切粘度和射流的体积电荷密度。从已报道的实验研究来看,纤维直径与纺丝液的这三个重要参数之间的幂指数与数学模型中的理论幂指数基本上不一致。导致这个结果的主要原因有:(1)非Newtonian流体已是主要的电纺丝对象,这三个数学模型都是以Newtonian流体而建立的;(2)这三个参数都不是独立变量等,并提出了静电纺丝在这方面的研究方向。     

丁醛等离子体处理填料对填充聚烯烃熔体流变性的影响

用毛细管流变仪研究了经丁醛等离子体处理的云母粉填充高密度聚乙烯熔体(160℃)和聚丙烯熔体(180℃)的流变性。数据表明,处理削弱填充聚烯烃熔体流动的非牛顿性,熔体流动非牛顿指数随等离子体处理时间的延长而增大;处理降低填充聚烯烃熔体在低切变速率下的表观粘度,提高其在高切变速率下的表观粘度,发生转变的临界切变速率对填充聚乙烯和聚丙烯分别为150S~(-1)和50S~(-1)。扫描电镜观察熔体形态证实,处理对熔体粘度的复杂影响,是处理改善填料在熔体中的分散性和提高填料与基体界面结合力两者综合作用的结果。     

聚硼硅氮烷的合成及其流变性能研究

以二氯甲基硅烷、三氯化硼、六甲基二硅氮烷为起始原料,采用缩聚法合成了一种新型SiBNC陶瓷先驱体-聚硼硅氮烷(PBSZ)。通过调节原料二氯甲基硅烷的用量可获得不同软化点的先驱体。通过改进的毛细管流变仪,首次对熔融纺丝状态时聚硼硅氮烷(PBSZ)的流变特性展开了研究。结果表明：PBSZ熔融纺丝时,剪切速率在10～110s-1时,为切力变稀流体。非牛顿指数为0.83～0.90,粘流活化能约为142KJ/mol,表观粘度440～2460Pa·s,PBSZ对温度变化的敏感性较聚碳硅烷小,可纺温区较宽。PBSZ纺丝性能良好,纤维连续无断头长度﹥1600m,纤维直径﹤20μm。     

Crystalline behaviors and phase transition during the manufacture of fine denier PA6 fibers

Recently we have successfully produced fine denier PA6 fibers by using additives containing lanthanide compounds. Meanwhile, crystallization and phase transition of PA6 fibers during spinning and drawing processes were investigated. During the spinning process, β phase crystal could be obtained in as-spun PA6 fibers which were produced with relatively high melt draw ratio, while γ phase crystal predominated when the melt draw ratio was relatively low. β phase crystal, whose behaviors are similar with those of γ phase by FT-IR and XRD characterization, could be transformed to α form easily when PA6 fibers are immersed in boiling water. However, γ phase crystal of PA6 remains unchanged in boiling water. Thus, β and γ phase crystals of PA6 can be differentiated by the crystalline behaviors of PA6 fibers after treatment in boiling water. Further experiments demonstrate that the β phase can also be produced during a drawing process where a phase transformation from γ to α occurs. In other words, β phase may act as an intermediate state during the phase transformation.     

聚丙烯熔体的零切变粘度与粘均分子量的关系

<正> 零切变粘度η_0是聚丙烯熔体流变性能的一个基本物理量,零切变粘度-分子量关系不仅具有理论上的兴趣,而且也有较大的实用意义。在文献中零切变粘度通常都是用毛细管粘度计数据外推求得的,但是由于聚丙烯熔体有较强的非牛顿性,即使在毛细管粘度计测量下限测得的粘度仍表现出明显的切变速率依赖性。因此,难于用外推的方法     

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.     

Melt flow behavior of polypropylene composites filled with multi-walled carbon nanotubes during extrusion

Polypropylene (PP) composites filled with multi-walled carbon nanotubes (MWCNTs) were prepared using a twin-screw extruder. The melt flow properties of the composites were measured with a capillary rheometer in a temperature range from 180 to 230 °C and at various apparent shear rates varying from 100 to 4000 s⁻¹. The results showed that the melt shear stress increased almost linearly while the melt shear viscosity decreased almost linearly with increasing shear rates in a bi-logarithmic coordinate system. The melt shear flow followed the power law relationship and the dependence of the melt shear viscosity on temperature obeyed the Arrhenius equation. The relationship between the melt shear viscosity and the MWCNT weight fraction was roughly linear under the investigated range of temperature or shear rate.     

细旦尼龙6纤维加工过程中的晶型转化行为

通过引入富镧稀土化合物等添加剂,成功实现了细旦尼龙6纤维的熔融纺丝．考察了在纺丝卷绕成型以及牵伸过程中尼龙6纤维的晶型变化．借助XRD和FT－IR等研究手段,发现尼龙6在纺丝过程中可以生成亚稳态的B晶型晶体．这种β晶型经过沸水处理后很容易转化为α晶型,而γ晶型尼龙6经沸水处理后不发生相转变．因此可以通过沸水热处理的方法区分尼龙6的β和γ晶型．在纤维的卷绕过程中,当熔体拉伸倍数较高时,尼龙6可能产生β晶型;当熔体拉伸倍数较低时,则以γ晶型为主．在纤维的牵伸过程中,γ晶型经过β晶型中间态向α晶型相转变．上述结果对于指导改进细旦尼龙6纤维的加工工艺以及提高产品性能有指导意义．     

熔体黏度对黏土在聚丙烯/聚苯乙烯共混物中优先插层行为的影响

通过熔融共混法在160℃加工条件下制备了聚丙烯/聚苯乙烯/黏土(PP/PS/clay)复合材料.X射线衍射分析(XRD)和透射电镜分析(TEM)的结果表明,黏土在共混物中存在着优先插层现象.黏土优先被PS分子链所插层,且不受PS组分含量和加料方式的影响.基于复合材料中PP和PS组分的熔体黏度对温度敏感性的差别,通过改变加工温度的方法,研究组分的黏度差别对黏土优先插层行为的影响.随共混加工温度的升高,黏土在共混物中的分布位置逐渐从PS相向PP相迁移.TEM和动态黏弹行为测试(ARES)的结果表明,组分间黏度的差别能控制黏土的优先插层行为.组分黏度越高,加工过程中所能传递的剪切应力就越大,插层能力也就越强.     

Melt flow behavior in capillary extrusion of nanometer calcium carbonate filled PCL bio-composites

Nanosized calcium carbonate (nano-CaCO₃) filled polycaprolactone (PCL) bio-composites were prepared by using a twin-screw extruder. The melt flow behavior of the composites, including the entry pressure drop, melt shear flow curves and melt shear viscosity, were measured through a capillary rheometer operated in a temperature range of 170∼200 °C and shear rates varying from 50 to 10³ s⁻¹. The entry pressure drop showed a non-linear increase with increasing shear stress when the filler weight fraction was less than 3%, while it decreased slightly with an increase of shear stress at a filler weight fraction of 4%. The melt shear flow roughly followed a power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Moreover, the influence of the nano-CaCO₃ on the melt shear viscosity of the PCL composite was not significant at low filler levels.     

Melt spinning of poly(l/d)lactide 96/4: Effects of molecular weight and melt processing on hydrolytic degradation

This study focused on determining the effects of molecular weight on the degradation of polylactide 96l/4d in melt spinning and the effects of melt processing on hydrolytic degradation. Three polylactides with different inherent viscosities were melt spun, and the fibres were studied in vitro. Results showed that during melt spinning high-molecular-weight polylactide degraded because polymer chains were subject to high shear stress and high melt temperatures, whereas a low-molecular-weight polylactide with low melt viscosity was not affected by melt processing. Most degradation occurred during the melting phase in the length of the extruder barrel. Lactide monomer, generated as the polymer degraded in the melt, significantly affected in vitro degradation such that the degradation rate was directly proportional to the lactide concentration of the polymer.