Correlation Between Structural and Dynamic‐Mechanical Transitions of Different Syndiotactic Polypropylene Polymorphs

Abstract

We prepared several well‐characterized syndiotactic polypropylene (sPP) polymorphs so as to correlate their thermal and dynamic‐mechanical behaviors. A sample was crystallized in pure form I at 100°C; a second sample containing only the trans‐planar mesophase was prepared by directly drawing a quenched sample at 0°C; a third sample, drawn at room temperature, contained both the trans‐planar mesophase and a fraction of the helical form II. By annealing this sample at increasing temperatures, we obtained a series of samples containing either trans‐planar mesophase, or form II and form I crystallinities.

In the dynamic‐mechanical analysis, the sample containing form I crystallinity showed only the amorphous glass transition, at 19°C, before melting at a high temperature. The trans‐planar mesophase transformed, at temperatures higher than 50°C, into the helical forms, and this transition was completed at 80°C. The dynamic mechanical curve of the sample containing only the mesophase showed a peak, centered at 50°C, which could be clearly associated to this transition. The sample containing the trans‐planar mesophase and the helical form II, showed in the dynamic‐mechanical curve a third peak that can be associated with the melting recrystallization of form II into the most stable form I. These results are important, because it was possible to directly correlate the structural transitions of the sPP polymorphs to the dynamic‐mechanical behavior. Moreover, a dynamic‐mechanical analysis could help recognize the presence of the trans‐planar mesophase or of the helical form II in more complex structural organizations.     

2-氨基苯硫酚NIR-SERS光谱及其在纳米银表面吸附行为分析

本文采用静电自组装的方法制备了二维纳米银膜。UV-vis吸收光谱显示其等离子体共振吸收带位于400+900nm的光谱范围,延伸到了近红外区,可以较好的匹配785nm的近红外激发光源。以该纳米银膜为基底,对2-氨基苯硫酚(2-ATP)分子进行了近红外表面增强拉曼散射(NIR-SERS)检测,获得了重复性良好的NIR-SERS光谱图。实验表明:以2-ATP为探针分子时,该纳米银膜的NIR-SERS增强因子达到2.19×109。同时,本文采用密度泛函理论(DFT),以B3LYP/6-31G为基函数,对2-ATP分子进行结构优化和普通拉曼光谱(NR)计算,发现理论值和实验值吻合较好。此外,对2-ATP的NIR-SERS谱带进行了归属分析,发现当2-ATP分子在纳米银表面吸附时,是以-SH基团吸附到银表面,且同时-SH基团会被纳米银氧化。     

Crystallization Behavior of Modified Polyester with Varied Macromolecular Architecture

Several modified polyesters with varied macromolecular architecture, such as branched poly(ethylene terephthalate) (PET) based on glycerol (GL) from 0.004 to 0.05 mol ratio as a branching agent, blocked and branched poly(butylene terephthalate)‐polyether containing poly(tetramethylene oxide) (PTMO) as soft segment and GL as a branching unit, as well as segmented poly(ethylene terephthalate)‐polyether,were prepared. Their crystallization behavior was studied by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized optical microscopy (POM). It was found that a small extent of branching may enhance the crystallization of poly(ethylene terephthalate), while high degrees of branching (0.035–0.05) could block the development of crystallization. On the other hand, for even a small extent of incorporation of GL in the more flexible poly(butylene terephthalate)‐polyether chains, no enhanced crystallization was observed; blocking of crystallization from a branching defect may play the main role. The introduction of PTMO in poly(ethylene terephthalate) chains to a small degree facilitated the nucleation and speeded crystallization, but decreased the melting points of the polymers. A small number of nuclei and the greater induction time were found for branched PETs. The spherulities developed in branched PETs were larger and more perfect than those in PET due to less truncation of spherulites resulting from fewer nuclei, whereas the size of spherulities in poly(ethylene terephthalate)‐polyether became smaller with the increase of PTMO.     

Rheological Behavior of Blends of Poly(Phenylene Sulfide) with a Thermotropic Liquid Crystalline Aromatic Poly(Ether Ester)

A new type of thermotropic liquid crystalline aromatic poly(ether ester) (PEE) was prepared from 1,3-bis(4′-carboxyphenoxy)benzene, 1,4-diacetoxybenzene, and p-acetoxybenzoic acid through a melt transesterification process. The rheological behavior of blends of poly(phenylene sulfide) (PPS) with PEE was studied using a high-pressure capillary rheometer with the shear rate range of 50 s^?1 to 3000 s^?1. The results show that according to the range of shear rate, the flow curves of PEE/PPS blends can be divided into three zones: a first shear-thinning zone (n < 1, “n” represents non-Newtonian indexes), a shear-thickening zone (n > 1), and a second shear-thinning zone (n < 1), and the former two zones are more obvious with the increase of PEE content or elevated temperature. In the second shear-thinning zone, the PPS melt is close to a Newtonian fluid at high temperature and high shear rate; meanwhile the non-Newtonian behavior of the PPS melt at high temperature is enhanced with the addition of PEE. The apparent viscosity of PPS melts sharply dropped after adding PEE, especially at relatively low temperature and low shear rate. The curve of apparent viscosity vs. shear rate starts to flatten out after adding PEE, suggesting that the addition of PEE lowers the sensitivity of PPS to shear rate. As the content of PEE increases, the activation energy of the viscous flow, ΔE_η, of PPS decreases, which means that adding PEE weakens the temperature sensitivity of the apparent viscosity of the PPS melt. It can clearly be seen that the addition of PEE is beneficial to the processing of PPS.     

Measurements of radon concentration in drinking water samples from Kastamonu (Turkey)

Concentration of ²²²Rn was determined in selected natural spring and tap water samples collected during spring and summer seasons from Kastamonu, Turkey. The aim of this work was to produce a map of the radon concentrations in water sources of the province and to determine any potential radiological risk for the local population. Radon measurements were performed by an AlphaGUARD radon gas analyser. The average radon concentrations were found to vary from 0.39±0.02 to 12.73±0.39 Bq l^?1 for natural springs and from 0.36±0.04 to 9.29±0.45 Bq l^?1 for tap water in spring, from 0.50±0.09 to 19.21±1.00 Bq l^?1 for natural springs and from 0.31±0.03 to 13.14±0.38 Bq l^?1 for tap water in summer. Furthermore, the results are compared with international recommendations and concentrations reported for other countries. Doses resulting from the consumption of these waters were calculated. The effective dose equivalents due to the intake of the ²²²Rn present in these waters are expected to range from 0.93 to 32.54 μSv y^?1 in summer and from 0.80 to 49.09 μSv y^?1 in spring.     

Zerstörungsfreie risstiefenbestimmung in Betonbauwerken mittels Radiotracerverfahren

At the Leipzig Technical University a method was developed, which allows to determine nondestructive the crack depth in concrete up to 15 cm. Based on a radiotracer technique the access to only one side of the object is required. The labelling of artificial-made cracks was carried out by use of a transport medium (not miscible with water) on the base of methyl isobutyl ketone (MIBK) and In- 113m as radionuclide. For the calculation of crack depth, measure-geometrical parameters were used. The improvement of the reliability of building-diagnostical interpretation using radio-physical parameters is described. A first application is provided for concrete structures below chemical equipments built as a barrier against ecologically harmful substances (petrol tanks). The intersectional aspect of further qualifications of the technique is emphasized.     

利用CdTe量子点增敏鲁米诺-过氧化氢化学发光体系测定水环境中的对苯二酚

在碱性条件下,CdTe量子点对鲁米诺-过氧化氢化学发光体系具有显著的增敏作用,而对苯二酚对该体系的化学发光有强烈的抑制作用,以此建立了流动注射化学发光检测对苯二酚的新方法。在优化实验条件下,在1.0～25 nmol·L-1范围内对苯二酚的浓度与化学发光强度的抑制值ΔI呈良好的线性关系(R2=0.993 2),检出限为0.76 nmol·L-1,经实际应用证明,该方法可用于水环境中对苯二酚的测定。此外,对CdTe量子点增敏鲁米诺-过氧化氢化学发光体系的机理进行了探讨。     

Order Parameter and Refractive Index of Cholesteryl Linoleate

Refractive indices of cholesteryl linoleate are determined at different temperatures and order parameters have been calculated in smectic and cholesteric phases.     

Effect of Alkyl Side Chain Length on Relaxation Behaviors in Poly(n-alkyl Acrylates) and Poly(n-alkyl Methacrylates)

Dynamic mechanical analysis (DMA) is used to investigate the effect of alkyl side chain length on the relaxation behavior of poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) above the glass transition temperature (T_g). Master curves and shift factors (log a_T) were obtained using the time–temperature superposition (TTS) principle. The log a_T curves of PnAA and PnAMA exhibit a dynamic crossover from one Vogel–Fulcher–Tammann–Hesse (VFTH) equation to another above T_g. The corresponding temperature was designated as the dynamic crossover temperature (T_c). It is found that T_c/T_g and the apparent activation energy (E_g) increases, e whereas the fragility index (m) decreases with increasing alkyl side chain length. Further analysis shows that m ∝ T_g, E_g∝ , and E_g∝ m² for both PnAA and PnAMA.     

Comparative Study of Tribological Properties of Polyphenylene Sulfide (PPS), Polyethersulfone (PES), and Polysulfone (PSU)

The tribological properties of polyphenylene sulfide (PPS), polyethersulfone (PES) and polysulfone (PSU), which have similar molecular structures, were investigated using an end-face contact tribometer and a reciprocating tribometer. The thermomechanical behavior of the polymers was analyzed using dynamic mechanical analysis (DMA). PPS exhibited a maximum friction coefficient with increasing load and sliding speed, while the friction coefficients of PES and PSU decreased only slightly. The wear rate of PPS was much lower than that of PES and PSU under high loads and speeds. It is suggested that the main factors influencing the friction and wear properties of the neat polymers are their condensed state and heat resistance. Amorphous PES and PSU showed liquid-like behavior and very low friction when the frictional surface was in the molten-flow state. The macromolecular crystals of crystallizable PPS give it some solid-like behavior and load-carrying capacity; hence PPS exhibited lower wear than PES and PSU.