Size-affected crystallization of trans-1,4-polybutadiene

By using different catalyst systems, two trans-1,4-polybutadiene (TPBD) samples with different tr trans-content and molecular weight were synthesized. The phase transition of two samples from monoclinic form to hexagonal phase was revealed by differential calorimeter scanning and X-ray, respectively. The small-angle X-ray scattering measurements showed the remarkable discrepancy of phase transition and melting point between the two samples was attributed to the different lamellar thickness of crystals: The crystals with different crystalline morphology and lamellar thickness were developed by casting different concentration TPBD solutions. Transmission electron microscopy morphology observations proved that annealing the specimen at the temperature above the phase transition point for different times resulted in the different lamellae thickening of monoclinic form. It means that annealing the TPBD in its hexagonal phase will also slightly favor the increase of both the phase transition temperature and melting point of hexagonal phase. (C) 2001 Elsevier Science Ltd. All rights reserved.

Crystallization behavior of PCL in hybrid confined environment

Poly(epsilon -caprolactone) (PCL) and silica (SiO2) organic-inorganic hybrid materials have been synthesized by the sol-gel method. The crystallization behavior of PCL in silica networks has been investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The degree of PCL crystallinity in PCL/SiO2 hybrid networks reduces with increase of SiO2. PCL is in an amorphous state when the concentration of PCL is lower than 40wt% in the hybrid system. The melting point of PCL in the networks is lower than, but close to that of pure PCL. WAXD and SEM results show that the crystalline behavior of PCL in PCL/SiO2 hybrid system is strictly confined. (C) 2001 Elsevier Science Ltd. All rights reserved.

用3种方法合成Y_3Al_5O_(12)∶RE~(3+)(RE=Eu,Dy)发光粉的对比研究

以金属硝酸盐为反应原料 ,分别采用柠檬酸 凝胶法、共沉淀法和固相法制备了YAG和YAG∶RE3+ (RE =Eu ,Dy) (1% ,摩尔分数 )发光粉 ,并通过XRD ,TG DTA和发光光谱对样品进行了表征。柠檬酸 凝胶法、共沉淀法和固相法制备的YAG和YAG∶Eu的晶相形成温度分别是 80 0和 90 0℃。Eu3+ 在非晶态和晶态YAG中其激发和发射光谱有明显差异 ,在一定温度范围内 ,发光强度随烧结温度的升高而增强。由于碳杂质的存在 ,90 0和 10 0 0℃下柠檬酸 凝胶法制备样品的发射强度较其他两种方法低。

Ca_2Y_8(SiO_4)_6O_2∶RE(RE=Eu,Tb)发光薄膜的制备及发光性能的研究

采用溶胶 凝胶法制备了稀土离子掺杂 (Eu3+ ,Tb3+ )的氧磷灰石三元稀土硅酸盐Ca2 Y8(SiO4 ) 6 O2 发光薄膜。通过X射线衍射 (XRD) ,红外光谱 (IR) ,扫描电镜 (SEM)等方法对薄膜的组成、结构、颗粒尺寸、形貌及厚度进行了研究 ,通过发光光谱对薄膜的发光性质进行了分析。XRD结果表明 70 0℃时薄膜尚处于非晶态 ,80 0℃时已开始有Ca2 Y8(SiO4 ) 6 O2 的物相形成 ,10 0 0℃时结晶已完全。这一点和红外光谱的结果相符。发光光谱测试表明Ca2 Y8(SiO4 ) 6 O2 ∶Eu3+ 薄膜显示了很强的红光发射 ,并以Eu3+ 的5D0 -7F2 (616nm)超灵敏跃迁为最强一组。Ca2 Y8(SiO4 ) 6 O2 ∶Tb3+ 的发射光谱由蓝光发射和绿光发射两部分组成 ,前者对应于5D3-7FJ,后者对应于5D4 -7FJ(J =6,5 ,4,3 ) ,且以5D4 -7F5(5 44nm)绿光发射为最强。

Enhanced crystallization and phase transformation of amorphous silicon nitride under high pressure

The crystallization and phase transformation of amorphous Si3N4 ceramics under high pressure (1.0-5.0 GPa) between 800 and 1700 degreesC were investigated. A greatly enhanced crystallization and alpha-beta transformation of the amorphous Si3N4 ceramics were evident under the high pressure, as characterized by that, at 5.0 GPa, the amorphous Si3N4, began to crystallize at a temperature as low as 1000 degreesC (to transform to alpha modification). The subsequent alpha-beta transformation occurred completed between 1350 and 1420 degreesC after only 20 min of pressing at 5.0 GPa. In contrast, under 0.1 MPa N-2, the identical amorphous materials were stable up to 1400 degreesC without detectable crystallization, and only a small amount of a phase was detected at 1500 degreesC. The crystallization temperature and the alpha-beta transformation temperatures are reduced by 200-350 degreesC compared to that at normal pressure. The enhanced phase transformations of the amorphous Si3N4, were discussed on the basis of thermodynamic and kinetic consideration of the effects of pressure on nucleation and growth.

Luminescence of RE2+ (RE = Sm, Yb) in barium octoborate

The reduction process from trivalent to divalent state for Sm3+ and Yb3+ ions in barium berates (BaB8O13) prepared in air was observed. The luminescence properties of these divalent rare-earth ions were studied. Yb2+ shows an f-d broad emission band, due to the 4f(14) --> 4f(13)5d transition, while the Sm2+ ion shows an f --> f transition. From the spectra of Yb2+, and using the D-5(0) --> F-7(0) transition of Sm2+ as a structural probe, two crystallographic sites were found to be available for the cations in the host. Vibronic transitions of Sm2+ were observed at low temperature. BaB8O13 was found to be a good host for reducing the trivalent rare-earth ions to divalent state and to exhibit interesting spectroscopic properties,

Non-isothermal crystallization kinetics of the poly(3-alkylthiophenes)

According to the data obtained from Differential Scanning Calorimetry (DSC),the method of Jeziorny, BOPOXOBCKHH and a new approach proposed by our laboratry are applied to study the nonisothermal crystallization behavior of poly( 3-dodecylthiophene) (P3DDT) and poly(3-octadecylthiophene) (P3ODT),and Kissinger method is used to get the value of the crystallization activation energy. The effect of the different alkyl substitution on crystallization is also investigated. In comparison to the methods of Jeziorny and BOPOXOBCKHH in which it can be found that the deviation from the line occurs in the later stage of crystallization, the new approach appears applicable due to the better linear relation. The values of the crystallization activation energy of P3DDT and P3ODT are estimated as 184.78kJ/mol and 246.93kJ/mol, respectivley, which implies that it is easiser to crystallize P3DDT than P3ODT.

The reduction of RE3+ in SrB6O10 prepared in air and the luminescence of SrB6O10 : RE2+ (RE=Eu, Sm, Tm)

The reduction of RE3+ to RE2+ (RE=Eu, Sm and Tm) in SrB6O10 prepared in air by high-temperature solid state reaction was observed. The luminescent properties of Eu2+ and Tm2+ show f-d transition and Sm2+ shows f-f transition at room temperature. Three crystallographic sites for Sm2+ in matrix are available. Vibronic transition of D-5(0)-F-7(0) of Sm2+ was studied. The coupled phonon energy about 108 cm(-1), was determined: from the vibronic transition. Due to the thermal population from D-5(0) level, (D1-FJ)-D-5-F-7 (J=0, 1, 2) transitions of Sm2+ were observed at room temperature. A charge compensation mechanism is proposed as a possible explanation.

Effect of physical aging on the microstructure and the crystallization of amorphous poly(aryl ether ether ketone ketone) (PEEKK)

Physical aging of poly(aryl ether ether ketone ketone) (PEEKK) has been investigated. Heat flow responses were measured after annealing the amorphous samples obtained by quenching the melt into an ice-water bath close to, but below, the glass transition temperature. The extent of aging is related to the supercooling from the glass transition temperature and to the aging time. The activation energy of the aging process, which was estimated by a Williams-Watt expression, is similar in magnitude to that obtained for the cold crystallization for the aged samples. The quenched glass is a metastable glass. The conformation of molecular chains rearranges with physical aging which results in the formation of a denser packing in the amorphous phase. The dense amorphous phase may form an initial nucleus for crystallization. Isothermal cold crystallization of the aged samples was carried out. The Avrami equation was used to determine the kinetic parameters, and the Avrami constant n is about 2. An Arrhenius expression was used to evaluate the activation energy of relaxation upon physical aging and the activation energy of transportation upon isothermal crystallization. The activation energy of relaxation is similar in magnitude to that of crystallization for aged samples. Results obtained are interpreted as kinetic effects associated with the glass formation process.

Miscibility and crystallization behavior of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB)/poly(ethylene oxide) (PEO) blends were studied by differential scanning calorimetry(DSC) and polarizing microscopy (POM). It is found that the miscibility is related to the composition of the blends. When the PEO content is over 20 percent, the miscible blends turn into partially miscible and the phase separation can be observed with POM. The addition of the PEO influences not only the morphology of PHB crystals and the radial growth rate of spherulites, but also the cold crystallization temperature.

Crystallization behevior of poly(3-dodecylthiophene)

The crystallization behavior of poly (3-dodecylthiophene) (P3DDT) is studied bq differential scanning calorimetry (DSC) under different cooling rates. When the methods of Jeziorny., Ozawa and a new one proposed by our laboratory are applied to describe its nonisothermal crystallization behavior, the new one is confirmed to be the best and convenient. By determining kinetic parameters, the analysis of the nonisothermal crystallization behavior is performed. According to Kissinger method, the crystallization activation energy of P3DDT is also evaluated.

Isothermal and non-isothermal crystallization kinetics of syndiotactic polypropelene

Isothermal and non-isothermal crystallization kinetics of a syndiotactic polypropylene(sPP) sample synthesized by new metallocene catalyst at different annealing temperatures and different cooling rates have been investigated by using differential scanning calorimetry(DSC) and density analysis. The equilibrium melting temperature( T-m(0)) is 158 degrees C by Hoffman-Weeks method. The equilibrium heat of fusion(Delta H-m(0)) is 88J/g in terms of the density analysis and DSC methods. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma = 5.2erg/cm(2) and sigma(e) = 69erg/cm(2), respectively. The work of chain folding is determined to be q = 33.75kJ/mol. Modified Avrami equation and Ozawa equation can be used to describe the non-isothermal crystallization behavior. And a new and convenient approach by combining the Avrami equation and Ozawa equation in a same crystallinity is used to describe the non-isothermal behavior as well. The crystallization activation energies are evaluated to be 73.7kJ/mol and 73.1kJ/mol for isothermal crystallization and non-isothermal crystallization, respectively. The Avrami exponent n is 1.5 similar to 1.6 for isothermal crystallization procedure, while the Avrami exponent n,is 2.5 similar to 3.5 for non-isothermal crystallization procedure. This indicated the difference of nucleation and growth between the two procedures.

Nonisothermal crystallization and melting behavior of poly(beta-hydroxybutyrate)-poly(vinyl-acetate) blends

Nonisothermal crystallization and melting behavior of poly(P-hydroxybutyrate) (PHB)-poly(vinyl acetate) (PVAc) blends from the melt were investigated by differential scanning calorimetry using various cooling rates. The results show that crystallization of PHB from the melt in the PHB-PVAc blends depends greatly upon cooling rates and blend compositions. For a given composition, the crystallization process begins at higher temperatures when slower scanning rates are used. At a given cooling rate, the presence of PVAc reduces the overall PHB crystallization rate. The Avrami analysis modified by Jeziorny and a new method were used to describe the nonisothermal crystallization process of PHB-PVAc blends very well. The double-melting phenomenon is found to be caused by crystallization during heating in DSC. (C) 1999 John Wiley & Sons, Inc.

Isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate)/poly(vinyl acetate) blends

The overall isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate) (PHB)/poly(vinyl acetate) (PVAc) blends were studied by using differential scanning calorimetry(DSC). The Avrami analysis indicates that the addition of PVAc into PHB results in the decrease in the overall crystallization rate of the PHB phase, but does not affect PHB's nucleation mechanism and geometry of crystal growth. The activation energy of the overall process of crystallization increases with the increasing PVAc content in the blends. The phenomenon of multiple melting endotherms is observed, which is caused by melting and recrystallization during the DSC heating run. (C) 1998 Elsevier Science Ltd. All rights reserved.

Structural analysis of nonlinearities of Ca4ReO(BO3)(3) (Re = La, Nd, Sm, Gd, Er, Y)

From the chemical bond viewpoint, second-order nonlinear optical (NLO) tensor coefficients of the family of new oxoborates Ca4ReO(BO3)(3) (CReOB, Re = La, Nd, Sm, Gd, Er, and Y) have been theoretically predicted. The d(11) tensor coefficient of CReOB is predicted to be -11 d(36)(KDP), which is the largest d(ij) tensor that has been found in borate crystals. From the structural characteristic of CReOB, we find the isolated BO33- clusters play a dominant role in contributions to the total nonlinearity, and the largest d(11) tensor of CReOB-type crystals is also ascribed to these BO33- clusters. We also find the NLO property of this family does not change dramatically for different rare-earth elements. The details of the calculation of CGdOB only are presented.