基于振动光谱成像技术的聚合物共混体系研究进展

振动光谱可以提供分子的振动信息,对于聚合物分子链的构象和链间的相互作用非常敏感。分子振动光谱成像作为一种原位无损检测技术,广泛应用于聚合物共混体系结晶、相态分布、界面扩散等性质的研究。本文综述了拉曼(Raman)光谱和红外(IR)光谱成像技术以及其衍生的具有高空间分辨率的红外-原子力联用技术(IR-AFM)、拉曼-原子力联用技术(Raman-AFM)以及针尖增强拉曼光谱技术(TERS)在聚合物共混体系研究中的最新应用进展,以探索并扩展振动光谱成像技术在高分子领域中的应用。     

光谱学研究硅烷钒锆复合钝化膜的结构和成膜机理

在热镀锌钢板表面制备了硅烷钒锆复合钝化膜。用X射线光电子能谱(XPS)、射频辉光放电发射光谱(rf-GD-OES)和傅里叶变换衰减全反射红外光谱(ATR-FTIR)表征了钝化膜的组成结构,分析了硅烷钒锆复合钝化膜的成膜机理。结果表明：硅烷之间互联构成了硅烷钒锆复合钝化膜的主成膜成分,无机缓蚀剂均匀分布在膜层中。钝化膜表面Si2p的XPS窄幅扫描谱100.7 eV处的拟合峰和红外光谱在波数1 100 cm-1 Si—O吸收峰变宽加强,表明硅烷以Si—O—Zn键的形式化学吸附在锌的表面,硅烷分子之间通过Si—O—Si键相互交联;红外光谱中1 650和1 560 cm-1的两个酰胺特征峰,结合910 cm-1的环氧特征峰的消失,表明γ-GPT的环氧基团在氨基活性氢的诱导下开环和γ-APT的氨基之间发生聚合反应形成交联的空间网状结构;rf-GD-OES分析发现钝化膜0.3 μm处存在一层富氧层,钝化反应生成的ZrF₄,ZrO₂和钒盐等无机物均匀分布在钝化膜中。分析膜层组成结构和成膜前后的ATR-FTIR光谱,研究了成膜过程中发生的物理过程和化学变化,提出了硅烷钒锆复合钝化膜的成膜机理。     

可逆光异构化双分子层及结构转变的振动光谱

通过吸收,荧光,FT红外,示差扫描量热和X光研究了双链二苯乙烯两亲分子的聚集和光异构化,获得了固态和两个溶液相的双分子层厚度,振动光谱显示在反式二苯乙烯双层的固态和溶液相中存在反式排列的氢键,而在用365nm光照后的溶液相中氢键主要是顺式排列的。亚甲基链伸缩振动则表明烷基链非常有序的排列。     

和频光谱研究萃取剂TOPO分子在空气/水界面处的取向行为

采用和频光谱研究了萃取剂TOPO分子在空气/水界面处的取向行为。研究发现,在不同膜压条件下,TOPO分子在水表面排布的有序化程度不同。膜压越大,TOPO分子在水表面的堆积密度越大,其分子碳链的取向越倾向于垂直空气/水界面。研究萃取剂分子在界面的取向行为,可以为理解界面处萃取剂分子与目标待萃取离子的相互作用机理提供思路。     

水杨醛类希夫碱在LB膜上的光谱性能的研究

合成了两种末端碳锭长度不同的水杨醛类希夫碱N-十二烷基（2-羟基-5-硝基苯甲亚胺）和N-十六烷基（2-羟基-5-硝基苯甲亚胺），研究了它们在气-液界面上的成膜性能，并通过紫外、荧光、红外显微镜等光谱手段对它们在LB膜上的性能进行了表征。实验结果表明两种希夫碱分子在LB膜中都形成了J-聚体，末端碳链较长的希夫碱 成膜性能相对较好，并且在膜上也能光致发光，但希夫碱分子的LB膜存在一定的缺陷。     

银岛膜表面胸腺嘧啶吸附行为的表面增强拉曼光谱和表面增强红外光谱研究

利用激光刻蚀法制备了具有化学纯净表面的银岛膜,该岛膜有很好的表面增强特性。利用表面增强拉曼光谱和表面增强红外光谱对胸腺嘧啶分子在银岛膜表面的吸附状态进行了对比研究。表面增强拉曼光谱中CN和C—O伸缩振动模式的出现表明胸腺嘧啶分子由原来的酮式结构变成了烯醇式结构;C(4)O伸缩振动谱带明显增强和N(3)的去质子化异构体特征峰的存在证明胸腺嘧啶分子是通过O(8)和N(3)的共同作用倾斜地吸附在银岛膜表面。对10-5 mol.L-1胸腺嘧啶在银岛膜表面上的红外光谱利用欧米采样器进行了反射法测量,发现其红外吸收增强了200倍。红外信号分析的结果支持了胸腺嘧啶分子通过O(8)与银表面发生相互作用的论断,同时也可得出胸腺嘧啶倾斜地吸附在银岛膜表面的结论。     

金属钴树状高分子与DNA相互作用的光谱法研究

通过氯化钴、乙二醛和第五代树状高分子反应合成了金属钴树状高分子配合物。并以亚甲基蓝为荧光探针,通过紫外-可见光谱、荧光光谱和同步荧光方法研究了金属钴树状高分子配合物与鲱鱼精DNA(hsDNA)的相互作用。结果显示,此配合物与hsDNA作用时,其紫外吸收产生明显增色效应,荧光强度增强。NaCl不同程度抑制金属钴树状高分子与hsDNA的结合。配合物也以竞争方式抑制亚甲基蓝与hsDNA作用,而亚甲基蓝可以插入金属钴树状高分子配合物的内部。这些结果证明,配合物主要通过与hsDNA链上带负电荷的磷酸基静电相吸形式结合而堆积在双螺旋hsDNA分子表面,减弱了结合位点附近亚甲基蓝分子与hsDNA的静电作用,而钠离子中和了hsDNA上磷酸基团上的负电荷,削弱了该配合物与hsDNA的静电结合。     

Au(111)表面甲基联二苯丙硫醇盐单层膜的原子结构

利用第一性原理研究了甲基联二苯丙硫醇盐(BP3S)单体、虚拟Au表面BP3S的分子链和单层膜及BP3S/Au(111)吸附系统的原子结构.计算表明BP3S单体呈对称结构,两苯环夹角为35°±10°.首先BP3S单体在虚拟Au(111)表面自组装成稳定的单一分子链.然后在虚拟Au(111)表面,分子链错位排列自组装成两种稳定的单层膜.在虚拟Au(111)-(3~(1/2)×7~(1/2))和Au(111)-(3~(1/2)×13~(1/2))表面,分子链与虚拟表面夹角分别为60°和30°.最后把两种稳定的单层膜吸附在Au(111)表面的四个吸附位,计算表明只有桥位和顶位稳定,且桥位的吸附能比顶位的吸附能低.比较吸附前后BP3S单层膜的结构变化,可知其变化不大,这说明吸附系统的结构参数主要取决于单层膜内的相互作用,衬底对其的影响不大.     

噻吩和3-甲基噻吩共聚膜及复合膜的红外光谱

采用扩散电流控制法,通过限制低氧化电位单体的浓度,从而限制它在高电位下的氧化电流,以达到减少它在聚合物中的相对含量的目的,成功地实现了噻吩(Th)和3-甲基噻吩(MTh)的电化学共聚。红外光谱及循环伏安测定分别表明,电化学共聚噻吩和3-甲基噻吩所制得的导电膜不是均聚物的共混物,共聚的方式也不是嵌段共聚,而更可能是无规共聚。此外,制备了噻吩/3-甲基噻吩导电复合膜,其吸波频率较单一导电聚合物有明显拓宽,在400cm-1～7000cm-1范围内有强的宽吸收。实验结果表明,复合膜的结构、层数、厚度以及层间微结构对红外吸收展宽效应都有影响。     

超二代微光像增强器多碱光电阴极膜厚测量研究

介绍了多碱光电阴极的光学性能和光谱反射率特性,测量了多碱阴极的光谱反射率曲线.该曲线与普通光学膜层光谱反射率曲线相比,形状较不规则,原因是多碱阴极膜层存在光吸收.光谱反射率曲线上的干涉峰是入射光在玻璃与阴极膜层界面反射和在阴极膜层与真空的界面反射的两束光发生干涉的结果.根据干涉的原理,如果阴极膜层所反射的两束光的光程差为二分之一波长的偶倍数时,光谱反射将出现干涉加强峰;如果阴极膜层所反射的两束光的光程差为二分之一波长的奇倍数时,光谱反射将出现干涉减弱峰.根据超二代像增强器光谱反射干涉峰对应的波长,可以计算出其阴极膜层的厚度约为191 nm,比二代像增强器阴极膜层的厚度增加了38％.多碱阴极膜层厚度是影响多碱阴极灵敏度的一个关键参量,仅仅靠人眼观察阴极膜层颜色的方法不准确.实践证明,利用光谱反射的方法来计算阴极膜层厚度的方法简单有效.如果在多碱阴极的制作过程中进行光谱反射率的监控,那么将可以精确控制阴极膜层的厚度,对多碱阴极的研究将会更加深入,多碱阴极的灵敏度也将会得到进一步的提升.     

CORRELATION AMONG MORPHOLOGY,INTERFACE, AND MECHANICAL PROPERTIES: EXPERIMENTAL STUDY

The effect of the disperse phase and the diffuse interface between phases on the tensile and impact strengths of polypropylene (PP)/poly(ethylene terephthalate) (PET) (75/20 by weight) blends compatibilized with maleic anhydride–grafted PP derivatives and on the tensile modulus of poly(vinyl chloride)/polystyrene (PVC/PS) nanoparticle blends compatibilized with polystyrene/poly(vinyl acetate) (PS/PVAc) block copolymers were investigated experimentally. The weight fraction of the diffuse interface between the PP and PET phases in the PP/PET blends was determined by modulated differential scanning calorimetry (MDSC). A correlation between the diffuse interface content and mechanical properties was found. With increasing diffuse interface weight fraction, the impact and tensile strengths of the PP/PET blends increased. There is a brittle-tough type transition in these PP/PET blends. With increasing diffuse interface content in the PVC/PS nanoparticle blends in which the particle size was fixed at about 100 nm, the tensile modulus also clearly increased.     

无规共聚物与均聚物共混体系的相容性

用核磁共振方法(NMR)及差示扫描量热法(DSC)测定了苯乙烯-丙烯腈(SAN)无规共聚物与均聚物系列聚甲基丙烯酸甲酯(PMMA),聚甲基丙烯酸乙酯(PEMA),聚甲基丙烯酸正丁酯(PnBMA),聚甲基丙烯酸异丁酯(PiBMA)共混体系的有关参数,比较全面地研究了影响SAN与聚甲基丙烯酸酯类(PMAs)相容性的因素,对它们相容性的本质进行了探讨,得出了一些重要结论.     

Phase Structure of Polyamide 6/Poly(styrene-co-acrylonitrile) and Poly(styrene-b-(ethylene-co-butylene)-b-styrene) or Poly(maleated Styrene/Ethylene-co-Butylene/Styrene) Ternary Blends

Two sets of ternary blends; polyamide 6/poly(styrene-co-acrylonitrile)/poly(styrene-b-(ethylene-co-butylene)-b-styrene) (PA6/SAN/SEBS) and polyamide 6/poly(styrene-co-acrylonitrile)/poly(maleated styrene/ethylene-co-butylene/styrene) (PA6/SAN/SEBS-g-MA), based on 70 wt% of matrix and 30 wt% of the dispersed phases at various concentrations of the minor components, were prepared via melt blending. Morphologies of the ternary systems were studied using scanning electron microscopy (SEM) and compared with the predictions of the spreading coefficient (SC), minimum relative interfacial energy (RIE), and dynamic interfacial energy (DIE) phenomenological models. The effects of different reported surface tensions of the used polymers and different protocols of the core-shell ratio calculation on the prediction of the models were investigated. The core-shell structure for PA6/SAN/SEBS system and two separate minor phases for PA6/SAN/SEBS-g-MA were observed at all of the compositions. The results indicated that the most important parameter for the accurate prediction of the models is the accurate calculation of the interfacial tension of the used polymers, in both the static and dynamic conditions.     

Transcrystallinity phenomena in PET and PAN fibres/polyhydroxybutyrate matrix systems

The interface in polyhydroxybutyrate/ PAN- and polyhydroxybutyrate/ PET fibres model composites has been investigated by polarizing optical and scanning electron microscopy. Under certain melting/cooling conditions in PAN fibre system a transcrystalline interphase is clearly observed, whereas in PET/PHB model composites the transcrystallization phenomenon occurs only when fibres with significant surface roughness are used.     

Chemically selective soft X‐ray patterning of polymers

The chemically selective modification of polymer mixtures by monochromated soft X‐rays has been explored using the high‐brightness fine‐focused 50 nm beam of a scanning transmission X‐ray microscope. Four different polymer systems were examined: a polymethylmethacrylate (PMMA) polyacrylonitrile (PAN) bilayer film; a PMMA‐blend‐PAN microphase‐separated film; a poly(MMA‐co‐AN) copolymer film; and a poly(ethyl cyanoacrylate) homopolymer film. A high level of chemically selective modification was achieved for the PMMA/PAN bilayer; in particular, irradiation at 288.45 eV selectively removed the carbonyl group from PMMA while irradiation at 286.80 eV selectively reduced the nitrile group of PAN, even when these irradiations were carried out at the same (x,y) position of the sample. In the last two homogenous polymer systems, similar amounts of damage to the nitrile and carbonyl groups occurred during irradiation at either 286.80 or 288.45 eV. This is attributed to damage transfer between the C[triple‐bond]N and C=O groups mediated by primary electrons, secondary electrons or radical/ionic processes, aided by their close spatial proximity. Although the overall thickness of the bilayer sample at 70 nm is smaller than the lateral line spreading of 100 nm, the interface between the layers appears to effectively block the transport of energy, and hence damage, between the two layers. The origins of the line spreading in homogeneous phases and possible origins of the damage blocking effect of the interface are discussed. To demonstrate chemically selective patterning, high‐resolution multi‐wavelength patterns were created in the PMMA/PAN bilayer system.     

Effect of Maleated Styrene/Ethylene-co-Butylene/Styrene on the Dispersed Particles Size and Mechanical Properties of Polyamide 6/Poly(styrene-co-acrylonitrile)/Poly(styrene-b-(ethylene-co-butylene)-b-styrene) Ternary Blends

In this study, the effect of several parameters, including composition, order of mixing, viscosity, and interfacial tension, on the phase structure and size of dispersed particles of polyamide 6 (PA6)/poly(styrene-co-acrylonitrile) SAN/poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) ternary blends was investigated. Moreover, the effect of addition of different ratios of reactive SEBS (maleic anhydride grafted-SEBS) and non-reactive SEBS at a fixed order of mixing and composition of 70/15/15 (PA6/SAN/SEBS + SEBS-g-MAH) on the mechanical properties of ternary blends was examined. Scanning electron microscopy (SEM) micrographs showed that among the studied parameters, interfacial tension and viscosity of dispersed phases were the leading factors in the formation of morphology and size of dispersed droplets. Mechanical results revealed that in contrast to the expectation, formation of core/shell structure of PA6/SAN/SEBS ternary blends did not result in a significant increasing of impact strength. The highest impact strength was achieved when a 50/50 weight ratio of SEBS/SEBS-g-MAH was used.     

Structure Formation of Blend and Sheath/Core Conjugated Fibers in High-Speed Spinning of PET,Including a Small Amount of PMMA

The blend of poly(ethylene terephthalate) (PET) and a small amount of polymer that has higher T _g than PET, such as polymethylmethacrylate (PMMA)—and is dispersed finely as immiscible particles in PET—exhibits lower molecular orientation than pure PET under high-speed fiber spinning. To obtain insight into the mechanism of the lower molecular orientation of the blend fiber, the sheath/core structure of PET (sheath)/PMMA (core) conjugated fiber (the same PET/PMMA weight ratio as in the blend fiber), was produced as a model. The thinning profile of the fiber diameter along the spinning line and the birefringence distribution of the cross-section were examined and compared among pure PET fiber, the conjugated fiber, and the blend fiber. The conjugated fiber had the lowest molecular orientation of PET in the sheath part, and its thinning process was accelerated similar to the blend fiber. As a result of the distribution of molecular orientation across the diameter of the conjugated fiber, it is considered that PMMA, having the high T _g , tends to solidify at a higher temperature (upstream) than PET in the thinning process, making the flow of PET accelerate as if it was pushed by PMMA. This causes the maximum dv/dx just before the solidification point to be smaller; therefore, the lower spinning stress, resulting in smaller birefringence of PET, can be considerable. This acceleration was generated at the interface of PET and PMMA, and spread toward the fiber surface as both polymers were thinning in elongational flow (in melt). On the other hand, close to the interface, molecules of PET were stretched by PMMA, resulting in an increase of birefringence. Such discussion is also considered to apply to the blend fiber. However, because the blend fiber had a significantly larger interface area compared with the conjugated fiber, it is considered that the increase of birefringence of PET by the interface drag force cannot be neglected. The larger particles of PMMA dispersed in PET results in the lower birefringence of PET that is supported by the elongation effect (i.e., the interface drag force).     

Glass Transition Behavior and Dynamic Fragility of PMMA-SAN Miscible Blend-Clay Nanocomposites

An investigation of the segmental dynamics and glass transition behavior of a miscible polymer blend composed of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) and its melt intercalated nanocomposite by dynamic mechanical analysis is presented. The principle goal was to address the effect of intercalation on local molecular structure and dynamics. The results showed that the intercalation of polymer chains in the galleries of organoclay (Cloisite 30B) led to a lower temperature dependence of the relaxation time (fragility) and activation energy of α-relaxation. Moreover, calculation of the distribution of the segmental dispersion showed a narrower dispersion in the glass transition region so that the Kohlrausch-Williams-Watts (KWW) distribution parameter (β_KWW) increased from 0.21 for neat PMMA to 0.34 for the 50/50 PMMA/SAN blend nanocomposite containing 3 wt% organoclay. Furthermore, the relaxation behavior of the blends showed a negative deviation from mixture law predictions based on the responses of the neat PMMA and SAN. These behaviors were attributed to the lack of specific interactions between the blend components (PMMA, SAN, and nanoclay layers) and the less cooperative behavior, i.e., less constraint for segmental relaxation, of the intercalated chains.     

Shear Effect on Morphology of Poly(Butylene Terephthalate)/Poly(Styrene‐co‐Acrylonitrile) Blends

Abstract

The shear flow effect on the morphology of poly(butylene terephthalate)(PBT)/poly(styrene‐co‐acrylonitrile)(SAN) was studied by a parallel plate type shear apparatus. In PBT/SAN = 20/80 blend, particle size of dispersed domains was governed by both break‐up and coalescence processes, and it was much affected by shear rate. The minimum particle size was observed at a certain shear rate. This phenomenon can be explained by the shear matching effect of PBT and SAN; that is, the viscosity ratio of PBT to SAN changed with shear rate and the finest morphology was obtained at the appropriate viscosity ratio. Similar behavior was also observed for PBT/SAN = 70/30 (PBT was the matrix), even though the particle size was larger than that of PBT/SAN = 20/80. For PBT/SAN = 10/90 blend, the sample showed a complicated appearance during shearing. A translucent region correlated to the fine morphology was observed more than twice with increasing shear rate. This phenomenon could not be explained by the viscosity matching effect only. It was affected by small changes in the balance of breaking‐up and coalescence effects.     

Unusual Phase Separation Kinetics in Poly(Methyl Methacrylate)/Poly(Styrene-co-Acrylonitrile) (PMMA/SAN) Blends with PMMA of Different Molecular Weights

The influence of molecular weight of poly (methyl methacrylate) (PMMA) on the thermodynamics and dynamics of phase separation in PMMA/poly (styrene-co-acrylonitrile) (SAN) blends was investigated via optical microscopy, time-resolved small-angle light scattering (SALS), and dynamic rheological measurements. It was found that the cloud point temperature of the blends decreased with an increase in the molecular weight of the PMMA. The phase separation rates of PMMA 48K/SAN and PMMA 85K/SAN blends with the near-critical composition were almost the same at small quench depths due to the limited mobility of molecular chains at low temperatures. However, an unexpected phase separation dynamics was observed at larger quench depths. Not only the morphology evolution but also the apparent diffusion coefficient D_app calculated from SALS revealed that the phase separation rate was faster in the PMMA 85K/SAN blend than in the PMMA 48K/SAN blend. The possible reasons for this unusual rapid kinetics of phase separation observed in the higher molecular weight blend were discussed in terms of molecular mobility and viscoelasticity.