聚左旋乳酸/聚氧化乙烯共混物的拉伸行为及结构转变

采用熔融共混方法制备了聚左旋乳酸(PLLA)和超高分子量聚氧化乙烯(PEO)共混物, 通过差示扫描量热(DSC)、 扫描电子显微镜(SEM)和二维广角X射线散射(2D-WAXS)等方法系统研究了PEO的加入对不同温度下PLLA拉伸行为及拉伸过程中微观结构变化的影响. 结果表明, PLLA/PEO共混物为非均相体系, PEO粒子均匀分布在PLLA中形成两相结构. PEO的加入能够显著降低PLLA的玻璃化转变温度(T_g), 在25～60 ℃范围内显著提高PLLA的拉伸性能. 在60 ℃拉伸时, PEO的加入提高了PLLA在拉伸过程中的结晶和形变能力. 在80 ℃拉伸时, 共混物的拉伸断裂伸长率下降, 但共混物的结晶速度仍高于纯PLLA样品.     

SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜研究

通过在磺化聚醚醚酮(SPEEK,DS=61.68%)中分别混入酚酞型聚醚砜(PES-C)、磺化酚酞型聚醚砜(SPES-C,DS=53.7%)制备出SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜.结果表明,共混的两种聚合物之间均具有较好的相容性.PES-C、SPES-C的混入能有效降低膜的溶胀及甲醇透过,且随着共混量的增加,这种作用越趋明显.纯SPEEK膜在75℃左右溶解,而SPEEK/PES-C(30wt%)、SPEEK/SPES-C(30wt%)共混膜在80℃时溶胀度仅为22.5%、26.32%.在室温至80℃范围内,纯SPEEK及共混膜的甲醇透过系数都在10-7cm2.s-1数量级上,远小于Nafion115膜.在饱和湿度下,温度大于90℃时,SPEEK/PES-C(20wt%)共混膜电导率超过Nafion115膜;温度大于110℃时,SPEEK/SPES-C(30wt%)共混膜电导率与Nafion115膜相当,达到0.11S.cm-1.高电导率,低透醇系数以及明显提高了的可使用温度表明该类共混膜有望在DMFC中使用.     

基于同步辐射超小角X射线散射的高密度聚乙烯空洞化行为研究

以一系列高温结晶后自然冷却的高密度聚乙烯(HDPE)为研究对象,利用同步辐射超小角X射线散射(USAXS)和示差扫描量热技术(DSC)对样品的微观结构进行了分析,并在线研究了单轴拉伸过程中的空洞化行为.结果表明,结晶温度高于110℃后自然冷却到室温的样品中存在热稳定性不同的两组片晶,等温过程形成结构完善的厚片晶,而在冷却过程会形成有缺陷的薄片晶,两组片晶的熔点分别在133和110℃附近.在30℃拉伸时,所有样品都可观察到空洞化并伴随发白现象.并且,等温结晶中形成片晶厚度越大的样品,相应的空洞化现象越明显.在拉伸过程中,空洞出现在屈服点附近,其法向方向平行于拉伸方向,后随应变的增加发生转向,法向方向与拉伸方向垂直.样品中空穴的长度为900~1200 nm.另一方面,随着冷却过程生成薄片晶比例的增加,空洞化趋势下降.此外,提高拉伸温度,样品更倾向发生塑性形变,空洞化程度减弱.     

EFFECT OF PARTICLE SIZE ON THE FILMING PROCESS OF POLYSTYRENE LATEX STUDIED BY AFM

The film formation process of micro-PS particles (diameter 742 nm) and nano-PS particles (diameter 29 nm) wasstudied by atomic force microscopy and differential scanning calorimetry. During a step heating process, the particles wereannealed for 0.5 h at each selected temperature. It was found that the deformation and interdiffusion temperatures of themicro-PS particles are ca. 120-130℃ and 140-150℃, that of the nano-PS particles are 90℃ and 100-110℃ respectively.The DSC traces of nano-PS particles showed that there was an exothermic peak near T_g after annealing for 0.5 h at theselected temperatures below 90℃; otherwise, the exothermic peak disappeared after annealing at 100℃ or above. Comparedwith the micro-PS pedicles, the sintering process of nano-PS particles occurs at much lower temperature determined by theconfined state of polymer chains with higher conformational energy in nano-particles, and completes in a much narrowertemperature range driven mainly by the larger total surface energy.     

Relationship between Localization of PBSU in Interlamellar/Interfibrillar Regimes and Double Peaks in DSC/SAXS in its Blend with PVDF

In this work, phase segregation and localization of PBSU have been investigated with the combination of SAXS and DSC in its blend with PVDF. After stepwise crystallization of PVDF and PBSU, there are double melting peaks of PBSU in DSC and double scattering peaks in SAXS. It has been demonstrated that double peaks can be attributed to the localization of PBSU in interlamellar/interfibrillar region in pre-formed PVDF crystal framework. In the case of low content of PBSU in blend, PBSU is trapped into the interlamellar region of PVDF crystals, resulting in the alternating lamellae crystal of them and the first peak (with low-q) in SAXS. The enhanced confinement effect produces thinner PBSU lamellae, corresponding to the lower melting temperature in DSC. Upon increasing its content in blend, some PBSU segregates in interfibrillar regions in addition to the enrichment in interlamellar regions of PVDF crystal framework. The larger space and higher concentration of PBSU in interfibrillar-regions contribute to periodic lamellae structure of PBSU with higher thickness, which is the reason for the second peak (with high-q) in SAXS and DSC. Our results not only clarify the relationship between localization of PBSU in interlamellar/interfibrillar regions and double peaks in DSC/SAXS, but also provide a novel strategy to detect the interlamellar and interfibrillar segregation of low-T_m component in miscible crystalline/crystalline blend.

     

聚环氧乙烷的双层片晶

聚环氧乙烷(M_n=7000)的双层片晶形态用透射电镜和差示扫描量热计进行了研究。在结晶温区54—56℃,现察到双层片晶,高于这个温区,同时看到双层片晶及单层片晶,低于这个温区,只看到单层片晶。双层片晶的熔点稍高于单层片晶。根据非整数次折迭链晶向整数次折迭链晶的转变,讨论了双层片晶和单层片晶的生长过程。在双层片晶界面上的H键降低了表面自由能,这是形成双层片晶的主要原因。     

Equilibrium Crystallization Temperature of Syndiotactic Polystyrene <Emphasis Type="Italic">γ</Emphasis> Form

The crystallization behavior of syndiotactic polystyrene (sPS) γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl's crystallization theory.On the basis of the differential scanning calorimetric results,it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness,which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization.Further temperature dependent small-angle X-ray scattering (SAXS) measurement revealed the evolution of the γ form lamellae upon heating until phase transition,involving three different regimes:lamellae stable region (25-90 ℃),melt-recrystallization region (90-185 ℃) and pre-phase transition region (185-195 ℃).As a result,recrystallization line,equilibrium recrystallization line and melting line were developed for the sPS γform crystallization process.Since the melt of γform involved a γto-α/β form phase transition,the melting line was also denoted as the phase transition line in this special case.Therefore,the equilibrium crystallization temperature and melting (phase transition)temperatures were determined at around 390 and 220 ℃ on the basis of the thermodynamic phase diagram of the sPS γform.     

Lamellar structural changes in miscible crystalline polymer blends during melting and crystallization processes,as studied by real‐time small‐angle X‐ray scattering measurements

Real‐time small‐angle X‐ray scattering (SAXS) measurement using synchrotron radiation was applied to study the lamellar structural changes in miscible crystalline polymer blends of poly(1,4‐butylene succinate) (PBSU) and poly(vinylidene fluoride) (PVDF) during melting and crystallization processes. The lamella of PBSU is either included in the interlamellar region of PVDF (interlamellar inclusion structure), or rejected from the interlamellar region of PVDF (interlamellar exclusion structure). The two lamellar structures coexists in the melt‐quenched samples of the PBSU/PVDF = 30/70 blend. Only the interlamellar exclusion structure exists in the drawn films of the PBSU/PVDF = 30/70 blend. The real‐time SAXS results show that the interlamellar exclusion structure in these samples is irreversibly transformed into the interlamellar inclusion structure by heating the sample above the melting temperature of PBSU and that the PBSU chains are crystallized between the lamellae of PVDF during the cooling process. The factors controlling the lamellar structural changes are possibly a balance of the miscibility and the chain exclusion by tie‐molecules and/or the chain diffusion under confinement by the lamellae of PVDF with higher melting temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1959–1969, 2007     

单色化X射线对薄膜表面高分子降解行为的影响

采用聚甲基丙烯酸甲酯(PMMA)和苯乙烯-丙烯腈无规共聚物(SAN)薄膜体系, 在不同的实验温度下, 研究了单色化的X射线对其中一个组分(PMMA)降解行为的影响.     

A calorimetric study of normal high density and ultra-high molecular weight polyethylene blends

The melting and the crystallization of blends of ultra-high molecular weight polyethylene (UHMWPE) and polyethylene high density with normal molecular weight (NMWPE) are investigated by means of differential scanning calorimetry (DSC). Mixing the components at a temperature below the flow temperature of UHMWPE (215 °C) results in segregated melting and crystallization. The segregated melting and crystallization temperatures of both components do not depend on composition of the blend. The extreme enthalpy dependence on blend composition is explained in terms of mutual influence exhibited by the components with respect to each other. It is due to the inner stresses in nonflowing UHMWPE characterized with a lot of entangled tie molecules. Mixing the components above the flow temperature of UHMWPE results in only one peak of melting and crystallization respectively. Complete mixing and probably co-crystallization between the components takes place on mixing NMWPE with flowing UHMWPE.     

Lamellar diffusion during heat treatment in meltcrystallized low-density polyethylene

The annealing behavior of low-density melt-crystallized polyethylene is discussed in terms of an unprecedented lamellar diffusion mechanism. For this purpose a combined small-angle x-ray diffraction (SAXS) and differential scanning calorimetry (DSC) study has been carried out. The presence of an initial double-lamellar population is directly evidenced by electron microscopy of freeze-cut and stained sections. The intercalation of thinner lamellae within the dominant wide-lamella population gives rise to an x-ray periodicity of 220 Å (structure I). The independent stacking of thinner lamellae within the material contributes to a second periodicity at 110 Å (structure II). During annealing at successively higher temperatures T_A, the low-molecular-weight components from the thin lamellae progressively diffuse out of the double population, reinforcing the stacks of thinner lamellae. At the melting temperature of the thinner crystals a complete segregation of these lamellae takes place, and a new periodicity (structure III) corresponding to stacks of collapsed thick lamellae emerges. The periodicity of structure III increases further with T_A. The thin lamellae of structure II can be extracted by a solvent, removing the corresponding SAXS peak and DSC maxima. The partial removal of thin lamellae from structure I by means of solvent extraction concurrently yields a decrease of the SAXS period. The present results suggest that molecular segregation of a low-molecular-weight fraction, contributing to the population of thinner lamellae, occurs during annealing.     

热处理条件对R-PET/LLDPE-g-MA共混物中PET玻璃化转变行为的影响

对回收聚对苯二甲酸乙二酯(R-PET)/LLDPE-g-MA马来酸酐改性的线性低密度聚乙烯共混物进行不同条件的热处理, 采用差示扫描量热仪(DSC)研究共混物基体PET的玻璃化转变行为. 结果表明, 当热处理温度低于PET的玻璃化转变温度(Tg)时, PET的玻璃化转变区域出现热焓松弛现象. 随着热处理温度的增加, PET的Tg逐渐升高; 在50~70 ℃下热处理48 h后, PET的Tg逐渐稳定. 当热处理温度高于PET的Tg而低于100 ℃时, PET的玻璃化转变区域出现2个热流转变, FTIR分析表明, PET分子构象开始发生变化. 当热处理温度为100 ℃时, DSC曲线上PET的玻璃化转变消失, PET的结晶度明显增加, 说明PET开始冷结晶的温度在90~100 ℃之间.     

聚氯乙烯-聚氧乙烯共混物的反相色谱研究

用反相色谱研究了聚氯乙烯与聚氧乙烯的相容性,发现其共混物的比保留体积V_g23具有重量加和性,表明共混物可能发生了相分离。导出了相分离体系聚合物相互作用参数X₂₃的近似关系式:X₂₃=(X₁₂-X₁₃)²/2,由此式可以解释X₂₃对探针种类的依赖性。聚氯乙烯和聚氧乙烯共混体系的反相色谱实验结果基本符合这一关系式。     

Crystal structure and thermal behavior of cold-crystallized poly(trimethylene terephthalate)

The structure and thermal behavior of cold-crystallized poly(trimethylene terephthalate) (PTT) are revealed in detail by DSC, AFM, TEM, and WAXD as well as in situ FTIR and SAXS techniques. There is no effect of crystallization temperature and initial state on the crystal modification, yet the morphology is strongly affected by these two factors. First, the small rod-like lamellae for PTT are obtained during the cold crystallization instead of the spherulites formed in the melt crystallization. Second, the edge-on lamellar orientation in thin films is identified during the cold crystallization. The thickness and the lateral width of rod-like lamellae get larger and larger with increasing crystallization temperature. Thin lamellar crystals assemble randomly when the cold-crystallization temperature is lower, while lamellar stacks composed of thicker lamellae are observed when the PTT was annealed at elevated temperature. Moreover, for the cold-crystallized PTT, the final melting temperature does not vary with the crystallization temperature. This phenomenon is explained by the structural improvement during the heating process. For the cold-crystallized PTT sample at lower temperature, three transitions occur when it is heated again: the relaxation of the rigid amorphous phase, the reorganization of molecules in the intermediate phase, and then the melt–recrystallization behavior. Those transitions finally lead to thicker lamellae besides a higher crystallinity before the final fusion. Therefore, the final melting peak of these lamellae is at the same temperature.     

Elongational rheometry of polyethylene terephthalate/bisphenol-a polycarbonate blends

The elongational deformation properties of polyethylene terephthalate (PETP) and bisphenol-A polycarbonate (PC) blends were determined using a Rutherford elongational rheometer. The effects of temperature (in the thermoelastic region) and strain rate were studied on blends containing up to 50% PC. Addition of low levels of polycarbonate permits the thermoelastic processing of PETP over a wider temperature range. PETP is particularly sensitive to changes in temperature. Over the range studied, the effect of strain rate on elongational deformation is not very marked. However, the deformation temperature changes the strain levels at which strain stiffening occurs, an important observation in respect of processing and optimisation of physical properties of uniaxially oriented products. The effect of the addition of a phenoxy resin on the blend was studied, and although TEM analysis suggests that it did not compatibilise the blend, it did increase the available extension at higher temperatures.     

Crystallization behavior of polypropylene/polycarbonate blends

Crystallization behavior and morphology of polypropylene (PP)/polycarbonate (PC) blends have been studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). In the study of non-isothermal crystallization of the blends, the phenomenon of multiple crystallization peaks of PP/PC blends was related to the blend morphology in which PP was the dispersed phase as small droplets in the PC matrix. The phenomenon of a single crystallization peak of the PP/PC blends was related to the blend morphology in which PP was a continuous phase; in that case the crystallization peak temperatures of the blends were higher than that of the PP. The isothermal crystallization kinetics of the PP and PP/PC (80/20) blend were described by the Avrami equation. The results showed that the Avrami exponent of the PP/PC (80/20) blend was higher than that of the PP, and the crystallization rate of the PP/PC (80/20) blend was faster than that of the PP. The crystallization rate of the PP and PP/PC (80/20) blend were calculated according to the Hoffmann theory. Both the PP and PP/PC (80/20) blend had maximum crystallization rates. The temperature at the maximum crystallization rate for the PP/PC (80/20) blend was higher than that of the PP.     

Transition from miscibility to immiscibility in blends of poly(methyl methacrylate) and styrene-acrylonitrile copolymers with varying copolymer composition: a DSC study

The glass transition and the structural relaxation processes have been studied in blends of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt.% blend of PMMA with the SAN copolymer containing 30 wt.% of AN is immiscible, while blends with copolymers containing between 13 and 26 wt.% of AN are miscible. Thus the upper limit of miscibility is between 26 and 30 wt.% of AN. The temperature dependence of the relaxation times of the conformational rearrangements of polymer chains around the glass transition have been determined in the blends and pure components by modelling DSC thermograms obtained after different thermal histories in each sample. The slope in the Arrhenius diagram logτ vs 1/T around the glass transition temperature is significantly smaller in the blend which is closer to the upper limit of miscibility than in the other miscible blends in which SAN copolymer contains less AN. The change of slope can be ascribed to a distribution in the glass transition temperatures of the different rearranging regions, reflecting the appearance of a microheterogeneity in the blend that cannot be detected as a double glass transition in the blend.     

丝素褐藻糖胶共混膜的结构与热性能

丝素是蚕丝的主要成分，是人类最早应用的天然蛋白质之一，作为性能优良的天然纤维一直用于纺织行业．近年来，丝素膜由于具有良好的透气透氧性和较少的炎症反应，尤其是对活体组织具有良好的生物相容性的特点，在生物工程和生物医学领域得到广泛地研究，被用作酶的固定化材料和哺乳动物细胞培养的基质、体外组织工程支架和抗凝血材料等．     

偏氟乙烯-四氟乙烯共聚物高取向薄膜的形态结构研究

聚偏氟乙烯(PVF₂)至少有四种晶相结构,即α、β、γ和δ相,PVF₂的压电性和热电性直接依赖其β相结构。 本工作报导以特殊的熔体拉伸方法制备不同组成偏氯乙烯(VF₂)和四氟乙烯(VF₄)的共聚物高取向薄膜与对其结构的研究结果。     

Study of Dynamic Rheological,Dynamic Mechanical and Creep Properties of Acrylonitrile Styrene Acrylate (ASA)/Zn+2poly(ethylene-co-methacrylic acid) Ionomer Blend

A new class of blend system comprising weather resistant acrylonitrile/styrene/acrylate (ASA) terpolymer and Zn-ionomer was developed. Based on Zn-ionomer content, the blend system either forms ‘mushroom’ or ‘brush’ type conformation which affected dynamic rheology, DSC, DMA and creep properties differently. Formation of ionic crosslinkings by Zn-ionomer in ‘brush regime’ as well as limited ionic crosslinkings in ‘mushroom regime’ resulted in different nature molecular chain relaxation response. The DSC endotherm peak and glass transition temperature were also influenced by the type of conformation and ion-dipole interaction between the blend components. The tan δ from DMA study also reflected the similar trend. The creep deformation behavior of the blend was found to be dependent on highly deformable Zn-ionomer content and with temperature. The Findley model analysis suggests the ionic crosslinkings may be the possible reason for controlled creep deformation of the blend.