聚甲基丙烯酸甲酯/镓纳米复合物的动力学弛豫行为

通过原位自由基聚合方法制备了聚甲基丙烯酸甲酯(PMMA)以及含镓(Ga)质量分数为11.3%和13.5%的PMMA/Ga纳米复合材料.在玻璃化转变温度及以上温区,利用能量耗散技术研究PMMA/Ga纳米复合物的动力学弛豫行为,发现随着Ga含量的增加,复合物的α弛豫峰移向高温但峰高降低.此外,还定量研究了Ga含量对PMMA/Ga复合物的α' 弛豫的影响,并作出了相应的解释. 关键词： 相对能量耗散 玻璃化转变 力学弛豫     

La基非晶合金β弛豫行为:退火和加载应变的影响

β弛豫行为是理解非晶合金扩散、塑性变形和玻璃转变行为的重要切入口.本研究以具有显著β弛豫行为的(La_0.6Ce_0.4)₆₅Al₁₀Co₂₅非晶合金为研究载体,利用动态力学分析仪,研究了加载频率、退火以及加载应变等因素对非晶合金β弛豫行为的影响.结果表明,随着加载频率的升高,非晶合金β弛豫峰向高温段移动.低于玻璃转变温度退火导致非晶合金β弛豫峰内耗值降低,非晶合金“缺陷”浓度降低,玻璃体系向更稳定状态迁移.随加载应变幅值增大,非晶合金β弛豫强度增大.本研究为进一步厘清非晶合金β弛豫起源提供新思路.     

表面增强拉曼光谱研究高分子共混物薄膜相结构

采用拉曼光谱法研究了由聚苯乙烯(PS)/聚甲基丙烯酸甲酯(PMMA)的四氢呋喃(THF)溶液在玻璃基板上旋转涂膜得到的共混物薄膜。应用显微共焦拉曼光谱,根据PS在1604,1585cm-1处苯环的伸缩振动峰和PMMA在1728cm-1处羰基的伸缩振动峰,可以确定薄膜(厚度约为800nm)表面海岛状相结构的组分分布信息。另外,还对210℃下PS/PMMA(30/70)共混物薄膜退火过程中表面的变化进行了分析。采用表面增强拉曼散射效应对高聚物的增强作用得到了薄膜(厚度约为400nm)的Raman光谱,并且成功地对其组成进行了分析。     

α-碘酸锂的电流弛豫和偏压场作用下表观介电常数弛豫行为

本工作较为详细地测定了静电场作用下α-碘酸锂的电流弛豫行为:在撤去c轴方向上的静电场后,从我们所用测量电流仪器的响应时间到某一t_k的区间内,放电电流服从(t/t₀)^-α的负幂次方律;而在t>t_k,其规律近似地为:(t/t₀)^{(-α′ln(t/t₀))}。相关的弛豫参数α,α′和t_k在有限的范围内,依赖于温度和施加电压的大小,也因样品不同而有差异。对将近十个样品进行了测试,结果表明,大多数晶体在尽可能小的电压下0.43≤α≤0.7,0.07<α′<0.09;上述的电流弛豫表达式与α-碘酸锂在偏压场作用下观察到的其它物理现象的弛豫行为,与在中子衍射加强和表观介电常数中的表现如出一辙;可以初步肯定各种现象的弛豫行为具有相同的物理根源。 关键词：     

PVPh/PEO共混物动力学演化过程的NMR研究

聚合物共混物中链段的慢取向运动与其玻璃化转变行为和宏观力学性质密切关联,而基于化学位移各向异性重聚的~(13)C CODEX(centerband-only detection of exchange)固体核磁共振(SSNMR)技术能够有效表征共混物中链段的慢取向运动.该文利用~(13)C CODEX NMR技术详细研究了相容性聚合物共混物聚乙烯基苯酚/聚氧乙烯(PVPh/PEO)中的刚性组分PVPh在较宽温度范围内的慢取向运动特性与玻璃化转变过程的关联.研究表明,在玻璃化转变起始温度以下,PVPh主链的分子运动被冻结,而侧基存在b-松弛的慢取向运动;在玻璃化转变起始温度附近,PVPh主链具有明显的慢取向运动,而且主链和侧基是一种协同的分子运动.该文利用NMR技术揭示了共混物中的玻璃化转变起止温度分别对应于高分子主链慢取向运动CODEX信号的开始和极大值处的温度.     

欧拉圆盘不同能量耗散机理之间的关联

本文研究了欧拉圆盘运动过程中盘厚度以及盘面与水平面夹角α两因素对能量耗散的影响. 得出圆盘厚度与直径之比x对能量变化中各项因子的影响: x很小时, 质心在竖直方向上的动能变化和重力势能变化是系统能量耗散的主要因素; 当x>0.4142时, 圆盘绕与之平行的轴的转动动能变化成为主要因素, 并给出圆盘厚度可忽略的条件. 模拟了滚动摩擦、空气黏滞等不同能量耗散方式与x,α的关系, 导出各种耗散方式在圆盘运动的过程中的转变规律, 并指出x=0.1733, α>18°时能量耗散形式为纯滚动摩擦, 这修正了文献[26]结论.     

锆基非晶合金的动态弛豫和应力松弛

非晶合金动态弛豫、变形和微观结构非均匀性之间的关联是非晶态物理领域重要研究内容之一.本文选取玻璃形成能力优良,热稳定性好的Zr₄₈(Cu_5/6Ag_1/6)₄₄Al₈块体非晶合金作为研究载体,借助于动态力学分析及应力松弛实验探究了温度和结构弛豫对非晶合金动态弛豫和变形行为的影响.研究结果表明非晶合金动态弛豫行为对温度极其敏感,随温度升高表现为等构型、老化、玻璃转变和晶化4个阶段.基于玻璃转变温度之下等温测试,结构弛豫行为导致非平衡高能量状态非晶合金向低能量状态迁移,内耗随时间演化规律可用Kohlrausch-Williams-Watts (KWW)扩展指数方程描述.此外,基于KWW方程和激活能谱等方法分析了模型合金应力松弛过程中非均匀结构激活,该过程涉及弹性变形向非弹性变形的转变.由于非晶合金存在微观尺度的结构非均匀性与能量起伏,变形单元的激活并非为单一特征时间,而是服从一定分布.通过考虑对数时间尺度和变形单元激活的特征时间分布分别为对称Gauss分布和非对称Gumbel分布,可...     

FTIR定量分析聚乙二醇/聚乙烯共混物组成

利用傅里叶转变红外光谱(FTIR)定量分析聚乙二醇/聚乙烯共混物组成,对特征谱带的选择,重叠峰的分离,数据的拟合处理作了详细讨论。采用1 378 cm-1处聚乙烯的复合峰与1 110 cm-1处聚乙二醇的复合峰强度比作为定量分析的基准,利用基于Beer-Lambert定律的理论拟合方程能较好的实现峰强度比与组分浓度的对应关系,可满足聚乙二醇/聚乙烯共混物组分的定量分析的要求。     

快冷Fe-Al合金中的原子缺陷弛豫

在多功能内耗仪上用自由衰减和强迫振动方法研究了不同Al含量淬火Fe-Al合金中的两个弛豫型内耗峰.结果显示：P1(180℃)和P2(340℃)两个内耗峰只出现在淬火样品的加热过程中,而在随后的冷却过程中不出现.P1峰是由在α和β(或γ)点阵上的空位组成的最近邻双空位偶极子在应力诱导下的重新取向产生的,其弛豫强度随Al含量非单调地变化,在大约25% Al(原子百分比,以下同)处出现最大值.Al含量较低的Fe-Al合金无 关键词： 空位 弛豫 Al含量     

稀土离子发光体系中能量传递和迁移模型的研究

基于以前综合V-F模型(考虑施主受主(D-A)能量传递)和B模型(考虑施主施主(D-D)能量迁移)而提出的V-F-B综合模型,对La_1-xEr_xF₃体系中Er³⁺离子四种低掺杂浓度下(x=0.001,0.003,0.01,0.02)295K时⁴S_3/2→⁴I_15/2发光的时间演化曲线成功地重新进行了数值拟合.结果表明该体系内D-A间交叉弛豫能量传递是偶极-偶极作用,作用常数C_DA为4.75×10^-41cm⁶/s,与Okamoto等人原用YT扩散模型得到的结果一致.而拟合得到的四个D-D平均跳跃时间τ₀粗略地与x_D^α次方(x_D为D离子浓度)成正比(α≈-1.237),并不遵从τ₀很小时与x_D的-2次方成正比的理论关系.同时,通过把D-D迁移和D-A传递同时同样地纳入V-F模型还粗略估计了D-D平均跳跃时间τ₀′的值,发现它与V-F-B给出的τ₀拟合值比较一致,说明V-F-B模型在一定近似程度上是内部自恰的、合理的. 关键词： 能量传递 能量迁移 跳跃时间 交叉弛豫     

Mechanical spectrum study of glass transition by a composite method

Normalized mechanical spectra of glycerol, 1,2-propanediol carbonate and poly(vinyl chloride)/di(2-ethyl-hexyl) phthalate (PVC/DOP) blends were studied in the temperature range from 100 to 300 K by a composite method. The dynamic glass transition was observed, which exhibits a peak of temperature-dependent loss modulus. The peak moves toward higher temperature with higher measuring frequency, which accords with the relaxation feature of the dynamic glass transition. Another characteristic temperature can be marked in the mechanical spectrum by the onset of storage modulus change, which is labeled as T_gm. T_gm is found to be nearly equal to the calorimetric glass transition temperature in glycerol, 1,2-propanediol carbonate and di(2-ethyl-hexyl) phthalate. As we expected, this onset temperature in the mechanical spectrum has an intimate relation with the calorimetric glass transition of materials, and it can be regarded as a representative when the calorimetric glass transition temperature is not available. Finally, normalized mechanical spectra of PVC/DOP blends with different PVC content were obtained and mechanical glass transition temperatures T_gm were determined.     

Dynamic mechanical characterization of relaxations in poly(oxymethylene), miscible blends,and oriented filaments

Multifrequency dynamic mechanical analysis (DMA) data were obtained for molded poly(oxymethylene) (POM) and its blends from-150°C to 150°C. Because of the high crystallinity, the assignment of the glass transition in POM has been controversial in the literature. Low and high glass transition temperature (T _g) phenolated compounds, including poly(vinyl phenol), were found to be miscible with POM. The shift of the β transition in the POM blends favors an assignment of the β transition detected at ?3°C(1 Hz), not the ?80°C γ transition, as the T _g in semicrystalline POM because the latter is invariant with diluent. The peak at the β transition in pure POM is weak and can only be seen clearly by DMA measurements on samples that have not “aged” at ambient temperature. This is further evidence that the β transition arises from a cooperative glass-transition-like motion. The γ transition is not influenced by aging because it is due to a concerted localized main chain motion. The β transition of an oriented POM filament can be seen in the DMA flexural loss spectrum at-18°C (1 Hz), but not in a tensile loss spectrum. The broad a relaxation was detected at about 110°C (1 Hz) in molded POM and its blends, while it was shifted to about 135°C in the higher crystallinity, oriented system. The α peak is also independent of diluent, consistent with a crystalline origin for this transition, as was proposed earlier.     

Thermally stimulated depolarization current studies of sulfonated polystyrene ionomers

A detailed study of thermally stimulated depolarization current (TSDC) was carried out to investigate dipolar relaxation and the charge storage phenomenon in films of sulfonated polystyrene (SPS) ionomers having lithium or potassium as counterions. Differential scanning calorimetry measurements were also applied as a complementary technique, mainly to follow the change of the glass transition temperature with the amount of sulfonated groups. It was observed that, since the glass transition does not change significantly with the amount of sulfonated groups, a cluster of multiplets is expected not to be formed in the range used in this work. TSDC of SPS samples polarized at temperatures higher than the glass transition temperature showed three peaks: one at lower temperature (peak β), an intermediate peak (peak α), and a third that appeared at a temperature coincident with the polarization temperature (peak ρ). Quantitative information about trapping–detrapping and dipolar relaxation and their corresponding activation energies was determined by fittings of the deconvoluted peaks with kinetic relaxation processes.     

Study on O-Terphenyl/Polystyrene Blends: How Plasticizer Affects the Glass Transition of Polystyrene?

The effect of plasticizer o-terphenyl on the glass transition of polystyrene was investigated by Fourier transform infrared spectroscopy from a new aspect. The peak areas of four conformation insensitive bands as a function of temperature were studied, these being assigned to the vibrational modes of main chain groups and side groups of polystyrene. It was shown that the reorientation relaxation temperature of the main chain around glass transition was lower than that of the side groups when polystyrene was plasticized by o-terphenyl. It was explained on the basis of cohesional entanglements of polystyrene chains. The reorientation relaxation region of the side groups was nearly the same as the macroscopically observable glass transition region of polystyrene, implying that the glass transition process of polystyrene was dominated by the reorientation of side groups.     

Activation Energy for the Glass Transition of a Confined Elastomer in HDPE/PP Blends

Blends of two highly crystalline polymers containing an elastomer were prepared to study the glass transition of the confined elastomer. The polymers chosen were high density poly ethylene (HDPE), polypropylene (PP), and two elastomers of a different nature: natural number (NR) and EPDM. The dynamic mechanical analyzer (DMA) technique was used to analyze the storage modulus of blends with elastomer content from 0% to 30% by weight, with the remainder made up of equal amounts of HDPE and PP, and blends with 10% of the elastomer, but varied ratios of polyolefins. We used the differentiation modification of the Arrhenius method in the kinetic analysis assuming an n‐order relaxation mechanism, which allowed detecting the percolation threshold of NR. Results indicate that both temperature and activation energy for glass transition (T _g ) are dependent on the types of polymers in the blend and blend composition. The T _g and E values of the unblended elastomers are higher than those in blends; this behavior is associated with the elastomer confinement and blend morphology.     

Effect of Poly(butyl acrylate)-g-poly(styrene-co-acrylonitrile)’s Core/shell Ratio on Mechanical and Thermal Properties of Poly(butyl acrylate)-g-poly(styrene-co-acrylonitrile)/α-methylstyrene-acrylonitrile Binary Blends

Poly(butyl acrylate)-g-poly(styrene-co-acrylonitrile) terpolymer (PBA-g-SAN) with different core/shell ratios and α-methylstyrene-acrylonitrile (α-MSAN) were mixed via melt blending (25/75, W/W). It was found that the core/shell ratio of PBA-g-SAN played an important role in the toughening of rigid α-MSAN. According to an analysis of the impact strength and the morphologies of the impact fractured surfaces, the optimum core/shell ratio with the highest toughening efficiency was 60/40. Considering the results of dynamic mechanical thermal analysis (DMTA), the blends retained the high glass transition temperature (T_g) of α-MSAN because of the immiscibility between the two components. Moreover, increasing the core/shell ratio did not result in sacrificing the heat distortion temperature of the blends, which was attributed to the almost unchanged high temperature T_g of α-MSAN. The tensile strength, flexural strength, and modulus declined slightly with the increasing core content of PBA-g-SAN, which suggested that the stiffness of the blends decreased with the increasing core/shell ratio. This study showed that 60/40 was the optimum core/shell ratio used for toughening modification; it achieved a good balance between mechanical and heat resistance performance.     

Viscosity,glass transition and activation energy of solid cis-polyisoprene and trans-polyisoprene blends

Blends of cis-polyisoprene (CPI) and trans-polyisoprene (TPI) have been prepared by solution casting to study viscosity, glass transition temperature and activation energy for the glass transition. The viscosity of blends having different weight ratios has been obtained through a single experiment measuring storage and loss modulus using the dynamic mechanical analyser technique. The glass transition temperature is determined through the temperature at which the minimum of temperature derivative curve of viscosity falls. The activation energy of glass transition and fragility index have been obtained by employing the Vogel–Fulchar–Tammann (VFT) equation by assuming non-Arrhenius behaviour of viscosity of polymer blends. Results indicate that both glass transition and activation energy for the glass transition are influenced by composition and crosslink density of the blend.     

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.     

Effect of physical ageing in thin glassy polymer films

We have studied the effect of physical ageing in thin supported glassy polystyrene films by using ellipsometry to detect overshooting in the expansivity-temperature curve upon heating of aged samples. Films with thickness 10-200 nm have been aged at 70^° C and 80^° C (below the bulk glass transition temperature). We observe clear relaxation peaks in the expansivity-temperature curve for films thicker than 18 nm but not for the 10 nm film. The intensity of the relaxation peak is inversely proportional to the film thickness, while the temperatures characteristic to the relaxation peak are almost independent of the film thickness. These observations are successfully interpreted by the idea that the surface layer of the order of 10 nm has liquid-like thermal properties. Received 28 October 2002 / Published online: 1 April 2003 RID="a" ID="a"Present address: Yokohama Research Center, Mitsubishi Chemical Corporation, 1000 Kamoshida-chou, Aoba-ku, Yokohama 227-8502, Japan; e-mail: kawana@rc.m-kagaku.co.jp     

Crystallisation and molecular mobilities in liquid and glassy states of a MXD6 polyamide

The dynamic of molecular mobilities occurring above and below the glass transition of a polyamide called MXD6 have been investigated on samples with different degrees of crystallinity. The fragility index (m) has been evaluated for a fully amorphous material and it was found that m = 180 classifies this material as fragile in regard to the strong-fragile glass forming liquid concept. For semi-crystalline samples, the results show two relaxation processes at the glass transition. One can be attributed to the molecular mobility existing in the free amorphous domain, and the second peak to a molecular mobility existing in a rigid amorphous domain as proposed by the '3-phase model'. The existence of these two phenomena does not allow a correct determination of the fragility index for such semi-crystalline materials by means of calorimetric investigation.