Strukturuntersuchungen an naßersponnenen Polyacrylnitrilfasern nach der Gefriertrocknung

Zusammenfassung An unterschiedlich verstreckten und hydrothermisch nachbehandelten, danach gefriergetrockneten Polyacrylnitril-Gelfasern (PAN) wurden Messungen der Röntgenkleinwinkelstreuung (RKWS), Röntgenweitwinkelstreuung (RWWS) und Tieftemperatur-Gassorption (TTGA) durchgeführt. Die RKWS-Messungen zeigen, daß sowohl in den isotropen als auch in den orientierten Proben eine exponentialstatistische Verteilung der Form und Größe der Inhomogenitäten (Hohlräume, Cluster) vorliegt, welche durch die Kohärenzlängel _c bestimmt wird. Eine erhöhte Röntgenabsorption wurde bei den verstreckten Proben festgestellt. Die Analyse der aus der Kohärenzlänge und den Volumsanteilen der Phasen berechneten charakteristischen RK WS-Parameter (z.B. innere Oberfläche, Durchschußlänge) ergibt, daß jede Behandlung der Gelfasern eine Zu- oder Abnahme der etwa gleich großen Hohlräume verursacht (nucleotic change). Das relative Ausmaß dieser Veränderungen wird besprochen.Der Vergleich mit den Ergebnissen der TTGA an den gleichen Fasern zeigt, daß die Tendenzen bei der spezifischen Oberfläche und dem Porenvolumen (Zu- bzw. Abnahme) bei beiden Methoden annähernd gleich sind. Die Absolutwerte des Hohlraumvolumens unterscheiden sich aber z.T. um den Faktor 40. Dies führt zur Schlußfolgerung, daß mit der RK WS Faserbereiche als Hohlräume erfaßt werden, die bei der TTGA nicht angezeigt werden, weil sie für das Meßgas unzugänglich sind.

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Structural studies on wet-spun freeze-dried polyacrylonitrile fibers

Summary Polyacrylonitrile fibers (PAN) were drawn to different extents, hydrothermally aftertreated, and at last freeze-dried. The products were studied by small angle X-ray scattering (SAXS), wide angle X-ray scattering (WAXS), and low temperature gassorption (LTGS). The SAXS data show that the shape and the size of the inhomogeneities (voids, clusters) have an exponential statistical distribution determined by the correlation lengthl _c, both in the isotropic fibers and in the fiber-oriented ones. It has also been observed that stretching always causes a higher X-ray absorption. An analysis of the characteristic SAXS parameters (e.g., internal surface, mean chord length), which were calculated from the correlation length and the volume fractions of the phases, evidences that in all samples an augmentation or diminution of the number of the voids with nearly the same shape and size takes place (nucleotic change). Its relative number has been pointed out.Comparison with the results of the LTGS investigations at the same fibers shows that the tendencies of the specific surface and porosity (increase, decrease) are approximately the same with both methods. However, the absolute values of void volume differ in some cases by the factor 40. This leads to the conclusion that the SAXS method records domains of these fibers as voids which are not registered by LTGS (voids not accessible for the gas).

Herrn em.o.Univ. Prof. Dr.Josef Schurz zum 70. Geburtstag gewidmet     

HYDROPHOBICITY OF CONTAMINATED SILICONE RUBBER SURFACES

Silicone rubber (SIR) shows superior performance when used outdoors, but its surface can be transformed frominherently hydrophobic to hydrophilic by the adsorption of contaminants. Al(OH)_3, Al_2O_3, quartz powder and active carbonwere selected as authentic contaminants. Hydrophobicity of the surface was determined using contact angle measurement.The results indicate that the adsorbability of the contaminants can strongly affect the hydrophobicity of contaminated SIRsurface. The increasing rate of contact angle of specimens contaminated by Al(OH)_3 was much faster than that by Al_2O_3 andquartz due to the adsorption of migrated low molecular weight (LMW) polydimethylsiloxanes. Specimens contaminated byactive carbon could achieve sunde hydrophobicity within 15 min because active carbon has high adsorbability. Surfaces ofcontaminated ultrapure SIR, polytetrafluoroethylene (PTFE) and glass remain hydrophilic because they contain no mobileLMW components. The addition of oligomeric polydimethylsiloxanes has little effect on the hydrophobicity of contaminantscovered on SIR surface.     

鞘磷脂和神经节苷脂对磷脂酰乙醇胺混合脂超分子体系液晶态立方相Im3m和Pn3m结构影响的研究

用磷脂酰乙醇胺(DEPE)、鞘磷脂(Sphingomyeline, Sph)、神经节苷脂(Gm1)和胆固醇(Chol)模拟了生物膜超分子体系液晶态结构, 通过用小角X射线衍射(SAXD)对混合脂体系液晶态结构进行了研究, 鉴定出了两种立方相: 即Im3m(Q²²⁹)和Pn3m(Q²²⁴)结构. 实验发现, 鞘磷脂的含量对DEPE膜的结构有一定的影响, 随着鞘磷脂浓度的增加, 混合脂体系的液晶态结构发生了由Im3m(Q²²⁹)到Pn3m(Q²²⁴)的变化. 神经节苷脂(Gm1)的含量对混合脂体系的液晶态结构也有一定的影响, 当神经节苷脂(Gm1)含量达到某一临界值时, 混合脂体系的液晶态结构发生了从Im3m(Q²²⁹)到Pn3m(Q²²⁴) 的变化. 当DEPE-Shp-Gm1超分子聚集体中含有胆固醇时, 胆固醇的极性头部(—OH)与磷脂酰乙醇胺(DEPE)、鞘磷脂(Shp)、神经节苷脂(Gm1)的极性头部通过氢键相互作用形成液晶态立方相Im3m(Q²²⁹)结构, 再通过疏水/亲水相互作用形成稳定的Pn3m (Q²²⁴)结构.     

Dipole moments of some substituted benzaldehydes. Conformational preference of substituents ortho to the aldehyde group

The dipole moments of a number of substituted benzaldehydes are measured in benzene solution. The angle which the dipole axis of the CHO group makes with the axis of rotation of the group is determined. The observed moments of the ortho-substituted benzaldehydes are compared with the moments calculated for free rotation as well as fors-trans ands-cis orientations of the -CHO group.o-Fluorobenzaldehyde exists mostly in thes-trans conformation.o-Chloro-,o-bromo-ando-nitro-benzaldehydcs also exist in thes-trans conformation; their observed dipole moments are even lower than the values calculated fors-trans forms, indicating mutual induction of the ortho substituents. Though 2,5-dichlorobenzaldehyde is expected to have the same dipole moment as benzaldehyde, the observed moment is significantly lower due to mutual induction of the ortho substituents. 2,5-Dimethylbcnzaldehyde has, however, almost the same moment as benzaldehyde. The dipole moment ofo-methoxybcnzaldchyde is considerably higher than the values calculated for boths-cis ands-trans conformations. An explanation is given for this.o-Hydroxybenzaldehyde exists exclusively in thes-cis form due to internal H-bonding.     

High-resolution solid-state MAS 73Ge NMR spectra of some organogermanes

High-resolution solid-state magic angle spinning (73)Ge NMR spectra of some organogermanium compounds were measured. Most tetrasubstituted germanes with identical substituents exhibited signals except for one case. Tetrasubstituted germanes with two kinds of different but somewhat similar substituents exhibited broad peaks. Trisubstituted germanes failed to show signals, indicating the importance of symmetry around germanium.     

MEASUREMENTS OF CHAIN INTERPENETRATION OF POLYMER GLASSES

The concept of entanglement provides the basis of our current understanding of the flow behavior of polymer melts, Current techniques developed to investigate the degree of interpenetration of polymer chains only provide indirectly the information of the degree of entanglement in a relatively large scale （several to tens of nanometer）. In this article, we report ^1H-NMR spectroscopy with dipolar filters under fast magic angle spinning for probing chain interpenetration of polymer glasses at the molecular level.     

含氟嵌段共聚物离聚体的合成表征及其性能研究

嵌段共聚物离聚体具有独特的形态和固体及溶液性质 ,在热塑性弹性体、极性材料与非极性材料共混相溶剂和粘度调节剂等领域具有十分广阔的应用前景 ,引起了人们的普遍关注 .文献报道较多的是聚苯乙烯 乙烯 丙烯[1] 、聚苯乙烯 乙烯 丁烯 苯乙烯[2 ] 、聚苯乙烯 异丁烯 苯乙烯[3 ] 等共聚物中 ,聚苯乙烯链段部分磺化后所得离聚体的合成与性质研究 .众所周知 ,含氟聚合物具有低表面能和高表面活性等特性 ,因而将含氟基团引入到嵌段共聚物离聚体中有望开发出一种新型的特殊功能材料 .原子转移自由基聚合 (ATRP)自 1 995年问世以来 ,已成功…     

Study of geometrical parameters in N-H...N type of hydrogen bonds

Geometrical parameters associated with N-H ... N types of hydrogen bonds have been analysed using crystal structure data on nucleic acids, amino acids and related compounds. Histograms depicting the frequency distribution of N-H ... N length (l) and H-N ... N angle (θ) have been drawn and conclusions on the favoured geometry of such bonds have been arrived at. The distribution ofl shows a pronounced maximum in the range between 2.9? and 3.0? with an overall average of 2.98 ?. The θ distribution shows a pronounced maximum for the hydrogen bond angle in the range 0°-10°, with a rapid fall-off in frequency for nonlinear hydrogen bonds. The frequency shows a cos⁶θ dependence as compared to cos²θ dependence term used earlier to predict the angular dependence of hydrogen bond potential energy in proteins and polypeptides.     

溶致液晶中金属纳米粒子的掺杂及其作用机制研究

在用琥珀酸二异辛酯磺酸钠(AOT)构建的具有长程有序结构的层状溶致液晶内, 用不同方式导入预制的亲油或亲水贵金属纳米粒子, 可得到纳米粒子分布在不同介观空间内的无机/有机杂合体. 依据小角X射线散射和偏光显微镜结果, 通过分析掺杂纳米粒子与液晶模板的相互作用, 对掺杂前后体系结构的变化及制得杂合体的稳定性进行了表征. 结果表明, 除考虑掺杂粒子与层状模板空间的匹配外, 体系中静电斥力、范德华引力和Helfrich涨落力之间的平衡是维持液晶结构稳定的基本条件.     

直链醇链长对层状液晶结构与稳定性的影响

作为助表面活性剂,直链醇在层状溶致液晶的制备中是非常重要的。本文以层状液晶的相行为和小角度X射线衍射测量,研究了直链醇链长对层状液晶结构与稳定的影响。