Devitrification of TeO2-doped fluoroaluminate glass

Crystallization behavior of the glass system AlF3-MgF2-CaF2-SrF2-BaF2-YF3-TeO2 (AMCSBY-TeO2) Was studied by the nonisothermal method using differential thermal analysis. The activation energy E and Avrami exponent n were determined by nonisothermal method. It is found that the value of E varies with increasing TeO2 and reaches a minimum at 10 mol fraction TeO2, while n decreases from 3.65 to 1.78 with the addition of TeO2. X-ray diffraction shows that Ba2Te3O8, MgTe2O5, and SrTeO3 phase formed when the glasses were reheated. The addition of TeO2 changes the crystallization mechanism and improves the stability of the fluoroaluminate glass.

剪切对聚烯烃结晶行为的影响——高分子结晶过程中中介相的研究

本论文通过POM、DSC、WXRD和SR-SAXS等一系列技术手段分别对剪切场下的等规立构聚丙烯（iPP）和间规立构聚丙烯（sPP）均聚物、乙烯-辛烯共聚物（PEcO）以及iPP/PEcO共混物的结晶结构和结晶动力学过程进行了系统研究。 剪切不能改变sPP的晶型，但能使得（200）晶面发生取向，同时，剪切导致片晶结构发生明显的取向。对剪切场下不同辛烯含量的PEcO的结晶研究发现：剪切对广角测试范围的结构影响较小，对小角测试范围的结构影响较大，说明乙烯-辛烯共聚物熔体在一定尺度范围的结构是比较稳定的。通过对iPP/PEcO共混物体系的研究，发现剪切速率的提高减少了结晶诱导时间，但剪切速率的变化以及共混物中组分的变化对球晶的生长速率没有明显影响。剪切可以诱导共混物中的iPP形成β晶型，并且含量随着剪切速率的增大而提高。剪切使得共混物中iPP结晶的微晶和片晶均发生了取向，片晶取向随着共混物中弹性体含量的增加而增大。 通过对剪切场下均聚物、共聚物以及共混物的结晶行为研究，发现剪切对于聚烯烃微晶尺寸、片晶厚度以及长周期有较小影响，但对微晶和片晶的取向有一定影响，对片晶的取向影响尤其显著。

OLED中空穴传输层NPB薄膜的结晶化行为研究

近年来，虽然有机电致发光材料和有机电致发光器件得到了广泛的研究，然而贯穿整个有机电致发光研究主线的稳定性问题仍是一个重要的议题。作为发光器件的主要组成部分，有机小分子薄膜的性能不仅由组成分子结构决定，而且还受到自身形态结构的制约。要解决有机材料的热稳定性问题，材料薄膜的形态结构是一个重要的影响因素。弄清有机小分子薄膜的形态结构和性能间的相互关系对于进一步提高器件性能（效率和寿命）是十分必要的。有机分子的热不稳定性表现在形态结构上主要是由非晶态到结晶态的转变，从而引起器件性能的不稳定。所以本文详细研究了一种典型的半晶性有机分子薄膜（同时也是最经常使用的有机小分子空穴传输材料之一）-NPB薄膜的结晶化相转变，分别从均相成核结晶化相转变和异相成核结晶化相转变两个角度来阐述。本文通过AFM、PLM、X射线衍射、DSC等实验方法和研究手段表征了NPB薄膜由非晶态到结晶态的相态转化，并从热力学上进行了分析。同时结合了实际OLED器件中的应用。本论文研究表明NPB分子是一种典型的半晶性小分子，非晶与结晶两种状态的并存导致热力学上的不稳定。本论文详细研究了NPB薄膜的均相成核结晶化相转变和异相成核结晶化相转变，并指出半晶性的NPB分子薄膜的均相成核结晶化存在一个临界结晶厚度，当薄膜厚度超过临界结晶厚度时才能发生结晶。并且临界结晶厚度的大小与基底温度有关。而NPB薄膜的异相成核结晶化转变则由于异核的引入结晶能的降低相对来说容易许多。本论文首次从理论角度归纳提出了均相成核结晶老化机制和异相成核结晶老化机制两种关系到OLED器件稳定性（老化问题）的机制。是为数不多的从薄膜形态角度来研究器件稳定性的一篇文章，对从材料化学角度深入理解OLED器件稳定性有着重要的意义。

剪切对iPP结晶行为的影响

在聚合物的生产加工过程中，样品会不可避免地受到剪切流动作用，剪切流动诱导聚合物结晶一直是高分子的基础领域之一。受到剪切作用后，聚合物分子链取向生成与静态结晶时不同结构形态的晶体。聚丙烯具有质量轻，耐热性、耐腐蚀性好及易进行各种成型加工等优点，是应用最广泛的工业化生产的聚合物之一。因此研究聚丙烯在外力场中的性质是目前的热点之一。本论文通过剪切仪，偏光显微镜，X一射线衍射仪，DSC等各种实验仪器和实验手段研究了剪切对添加不同含量β成核剂的聚丙烯的晶体形态和晶体结构的影响；剪切对等规聚丙烯晶体形态、结晶动力学的影响以及振荡剪切对等规聚丙烯晶体形态和晶体结构的影响。通过对实验结果的分析研究，我们发现在134 ℃结晶时，对不同β成核剂含量的样品，成核剂含量越高，晶体尺寸越小，密度越大；并且样品的结晶温度越高。对样品施加剪切后我们发现虽然不同含量成核剂的样品中β晶的生成机制不同，但剪切都会抑制β晶的生成。同样的，在其他结晶温度，剪切也会抑制β的生成。通过不同的剪切方法，我们发现松弛是影响剪切诱导聚丙烯结晶行为的重要因素。采用适当的剪一切方法可以改变iPP晶体形态，生成纤维晶，增加晶体密度；并且可以力Fl速球晶生长速率。对实验结果进行拟合发现修正的Lauxizen-Hoffinan理论可以很好的用于描述剪切之后iPP的球晶生长结晶动力学。我们认为剪切加速结晶速度的原因是剪切增加了iPP熔体的自由能，利用DE-IAA模型计算得到的△G_f与实验结果基本一致。同时我们发现通过Arrhennius公式推导得到的iPP结晶温度范围内的零剪切粘度刃。适用于修正后的Laulizen-Hoffnan结晶动力学理论。我们通过分别变化应变和频率测定了振荡对iPP结晶行为的影响，结果发现在一定的频率下，应变对iPP形态影响很大，当应变达到200％时，生成纤维晶。并且随着应变的增加，iPP的晶体密度增加，而且分子取向明显增加。固定应变（100%），改变频率，我们发现在低频率时随着频率的增加，球晶密度增加，而后频率继续增加，球晶密度变化不大；并且频率的变化对iPP晶体形态没有影响，只生成球晶。另外振荡剪切同样能够诱导聚丙烯生成β晶，在一定的频率下，随着应变的增加，β晶结晶度增加；但是固定应变，增加振荡频率，我们发现p晶结晶度几乎不随着频率的变化而变化。

Blends of Poly(lactic acid) with Thermoplastic Acetylated Starch

Blends of poly(lactic acid)(PLA) and thermoplastic acetylated starch(ATPS) were prepared by means of the melt mixing method. The results show that PLA and ATPS were partially miscible, which was confirmed with the measurement of T-g by dynamic mechanical analysis(DMA) and differrential scanning calorimetry(DSC). The mechanical and thermal properties of the blends were improved. With increasing the ATPs content, the elongation at break and impact strength were increased. The elongation at break increased from 5% of neat PLA to 25% of the blend PLA/ATPS40. It was found that the cold crystallization behavior of PLA changed evidently by addition of ATPS. The cold crystallization temperature(T-cc) of each of PLA/ATPS blends was found to shift to a lower temperature and the width of exothermic peak became narrow compared with that of neat PLA.

Poly(ethylene glycol-co-propylene glycol) as a Macromolecular Plasticizing Agent for Polylactide: Thermomechanical Properties and Aging

Finding a Suitable plasticizer for polylactide (PLA) is necessary to overcome its brittleness and enlarge its range of applications. In this study, commercial PLA was melt-blended with a new plasticizer, an ethylene glycol/propylene glycol random copolymer [poly(ethylene glycol-co-propylene glycol) (PEPG)] with a typical number-average molecular weight of 1.2 kDa and an ethylene glycol content of 78.7 mol %. The thermal properties, crystallization behavior, and mechanical properties of the quenched blends and the properties of the blends after storage for 2 months under the ambient conditions were investigated in detail. The advantage of using PEPG is that it does not crystallize at room temperature and has good compatibility with PLA. The quenched PLA/PEPG blends were homogeneous and amorphous systems. With an increase in the PEPG content (5-20%), the glass-transition temperature, tensile strength, and modulus of the blends decreased, whereas the elongation at break and crystallizability increased dramatically. The cold crystallization of PLA resulted in phase separation of the PLA/PEPG blends by annealing of the blends at the crystallization temperature.

Synthesis and morphology of polyethylene chains grafted onto the surface of crosslinked polystyrene microspheres

The bifunctional comonomer 4-(3-butenyl) styrene was used to synthesize crosslinked polystyrene microspheres (c-PS) with pendant butenyl groups on their surface via suspension copolymerization. Polyethylene chains were grafted onto the surface of c-PS microspheres (PS-g-PE) via ethylene copolymerizing with the pendant butenyl group on the surface of the c-PS microspheres under the catalysis of metallocene catalyst. The composition and morphology of the PS-g-PE microspheres were characterized by means of Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy. It is possible to control the content of PE grafted onto the surface of c-PS microspheres by varying the polymerization time or the initial quantity of pendant butenyl group on the surface of c-PS microspheres. Investigation on the morphology and crystallization behavior of grafted PE chains showed that different surface patterns could be formed under various crystallization conditions. Moreover, the crystallization temperature of PE chains grafted on the surface of c-PS microspheres was 6 degrees C higher than that of pure PE. The c-PS microspheres decorated by PE chains had a better compatibility with PE matrix.

The morphology and thermal properties of multi-walled carbon nanotube and poly(hydroxybutyrate-co-hydroxyvalerate) composite

Nanocomposites based on poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) and multi-walled carbon nanotubes (MWNTs) were prepared by solution processing. Ultrasonic energy was used to uniformly disperse MWNTs in solutions and to incorporate them into composites. Microscopic observation reveals that polymer-coated MWNTs dispersed homogenously in the PHBV matrix. The thermal properties and the crystallization behavior of the composites were characterized by thermogravimetric analysis, differential scanning calorimetry and wide-angle X-ray diffraction, the nucleant effect of MWNTs on the crystallization of PHBV was confirmed, and carbon nanotubes were found to enhanced the thermal stability of PHBV in nitrogen.

Study on crystalline morphology of poly(L-lactide)-poly(ethylene glycol) diblock copolymer

Crystallization behavior, structural development and morphology evolution in a series of diblock copolymers Of poly(L-lactide)-blockpoly(ethylene glycol) (PLLA-b-PEG) were investigated via differential scanning calorimetry, wide-angle X-ray diffraction, polarized optical microscopy and atomic force microscopy. In these copolymers, both blocks are crystallizable and biocompatible. It was interesting that these PLLA-b-PEG diblock copolymers could form spherulites with banded textures, which was undercooling dependent. Single crystals with an abundance of screw dislocations were also observed via AFM. Such results indicated that these ringed spherulites and single crystals were formed during the crystallization of the PLLA blocks.

Preparation of fully cross-linked CNBR/PP-g-GMA and CNBR/PP/PP-g-GMA thermoplastic elastomers and their morphology, structure and properties

Binary CNBR/PP-g-GMA and ternary CNBR/PP/PP-g-GMA thermoplastic elastomers were prepared by reactive blending carboxy nitrile rubber (CNBR) powder with nanometer dimension and polypropylene functionalized with glycidyl methacrylate (PP-g-GMA). Morphology observation by using an atomic force microscope (AFM) and TEM revealed that the size of CNBR dispersed phase in CNBR/PP-g-GMA binary blends was much smaller than that of the corresponding CNBR/PP binary blends. Thermal behavior of CNBR/PP-g-GMA and CNBR/PP blends was studied by DSC. Comparing with the plain PP-g-GMA, T, of PP-g-GMA in CNBR/PP-g-GMA blends increased about 10degreesC. Both thermodynamic and kinetic effects would influence the crystallization behavior of PP-g-GMA in CNBR/PP-g-GMA blends. At a fixed content of CNBR, the apparent viscosity of the blending system increased with increasing the content of PP-g-GMA. FTIR spectrum verified that the improvement of miscibility of CNBR and PP-g-GMA was originated from the reaction between carboxy end groups of CNBR and epoxy groups of GMA grafted onto PP molecular chains. Comparing with CNBR/PP blends, the tensile strength, stress at 100% strain, and elongation at break of CNBR/PP-g-GMA blends were greatly improved.

Formation of a unique crystal morphology for the poly(ethylene glycol)-poly(epsilon-caprolactone) diblock copolymer

The crystallization behaviors of the poly(ethylene glycol)-poly(epsilon-caprolactone) diblock copolymer with the PEG weight fraction of 0.50 (PEG(50)-PCL50) was studied by DSC, WAXD, SAXS, and FTIR. A superposed melting point at 58.5 degrees C and a superposed crystallization temperature at 35.4 degrees C were obtained from the DSC profiles running at 10 degrees C/min, whereas the temperature-dependent FTIR measurements during cooling from the melt at 0.2 degrees C/min showed that the PCL crystals formed starting at 48 degrees C while the PEG crystals started at 45 degrees C. The PEG and PCL blocks of the copolymer crystallized separately and formed alternating lamella regions according to the WAXD and SAXS results. The crystal growth of the diblock copolymer was observed by polarized optical microscope (POM). An interesting morphology of the concentric spherulites developed through a unique crystallization behavior. The concentric spherulites were analyzed by in situ microbeam FTIR, and it was determined that the morphologies of the inner and outer portions were mainly determined by the PCL and PEG spherulites, respectively. However, the compositions of the inner and outer portions were equal in the analysis by microbeam FTIR.

Effects of reinforcement filler and temperature on the stability of beta-crystal in glass bead filled polypropylene

The effects of crystallization temperature (T,), glass bead content and its size on the, formation of beta-crystal and structural stability of originally formed beta-crystal in glass bead filled polypropylene (PP) were examined. The differential scanning calorimetry (DSC) measurements indicated that the amount of beta-phase in PP crystals was a function of the crystallization temperature and glass bead content. For a constant crystallization temperature, it was observed that the amount of beta-crystal initially increased with increase in glass bead content up to 30 wt.%, and then decreased slightly with further increase in the filler content. From the DSC data, a disorder parameter (S) was derived to define the structural stability of originally formed beta-crystals. The structural stability of originally formed beta-crystals was enhanced with increase in either the crystallization temperature or the glass bead content. Also, the influence of glass bead size (4-66 mu m) on the formation and stability of beta-crystals in PP/glass bead blends was studied. Large glass bead particles suppressed the formation and decreased the stability of beta-crystals.

Synthesis and characterization of maleated poly(3-hydroxybutyrate)

Graft copolymerization of maleic anhydride (MA) onto poly(3-hydroxybutyrate) (PHB) was carried out by use of benzoyl peroxide as initiator. The effects of various polymerization conditions on graft degree were investigated, including solvents, monomer and initiator concentrations, reaction temperature, and time. The monomer and initiator concentrations played an important role in graft copolymerization, and graft degree could be controlled in the range from 0.2 to 0.85% by changing the reaction conditions. The crystallization behavior and the thermal stability of PHB and maleated PHB were studied by DSC, WAXD, optical microscopy, and TGA. The results showed that, after grafting MA, the crystallization behavior of PHB was obviously changed. The cold crystallization temperature from the glass state increased, the crystallization temperature from the melted state decreased, and the growth rate of spherulite decreased. With the increase in graft degree, the banding texture of spherulites became more distinct and orderly. Moreover, the thermal stability of maleated PHB was obviously improved, compared with that of pure PHB.

Ring-opening polymerization and block copolymerization of L-lactide with divalent samarocene complex

Divalent samarocene complex [(C5H9C5H4)(2)Sm(tetrahydrofuran)(2)] was prepared and characterized and used to catalyze the ring-opening polymerization of L-lactide (L-LA) and copolymerization of L-LA with caprolactone (CL). Several factors affecting monomer conversion and molecular weight of polymer, such as polymerization time, temperature, monomer/catalyst ratio, and solvent, were examined. The results indicated that polymerization was rapid, with monomer conversions reaching 100% within 1 h, and the conformation of L-LA was retained. The structure of the block copolymer of CL/L-LA was characterized by NMR and differential scanning calorimetry. The morphological changes during crystallization of poly(caprolactone) (PCL)-b-P(L-LA) copolymer were monitored with real-time hot-stage atomic force microscopy (AFM). The effect of temperature on the morphological change and crystallization behavior of PCL-b-P(L-LA) copolymer was demonstrated through AFM observation.

Compatibilization of polyamide-6/syndiotactic polystyrene blends using styrene/glycidyl methacrylate copolymers

Blends of polyamide-6 (PA6) with syndiotactic polystyrene (sPS) were prepared using a series of styrene/glycidyl methacrylate (SG) copolymers as compatibilizers. These copolymers are miscible with sPS, and the epoxide units in SG are capable of reacting with PA6 end groups. These copolymers thus have the potential to form SG-g-PA6 graft copolymers at the PA6/sPS interface during melt processing. This study focuses on the effects of functionality and concentration of the compatibilizer on the morphological, mechanical and crystallization behaviors of the blends.. In general, SG copolymers are effective in reducing the sPS domain size and improving the interfacial adhesion. About 5 wt% glycidyl methacrylate (GMA) is the optimum content in SG copolymer that produces the best compatibilization. Both the strength and modulus of the blend have been improved on addition of the SG copolymers, accompanying a loss in toughness when higher concentration copolymer is added. Incorporation of SG compatibilizers to PA6/sPS blend has little influence on the crystallization behavior of PA6 component but resulted in a steady reduction in intensity of crystallinity peak of sPS and simultaneous crystallization of sPS with PA6 is observed.