Bi2—xPbxSr2Ca2Cu3Oy系高Tc超导体相变的研究

用DSC研究了高T_e超导体B_(2-r)Pb_rSr_2Ca_2Cu_sO_v(x=0,0.2,0.4,0.6)从室温至600℃范围内的相变。在320℃和440℃附近有二个吸热蜂,每一个峰对应一个相变过程。440℃附近的相变是不可递的,其原子激活能为1.37eV,是由高T_e相向低T_e相的转变。而320℃附近的相变则与超结构的形成有关。     

Reaction kinetics modeling and thermal properties of epoxy–amines as measured by modulated‐temperature DSC. II. Network‐forming DGEBA + MDA

Reaction‐induced vitrification takes place in the network‐forming epoxy–amine system diglycidyl ether of bisphenol A (DGEBA) + methylenedianiline (MDA) when the glass‐transition temperature (T_g) rises above the cure temperature (T_cure). This chemorheological transition results in diffusion‐controlled reaction and can be followed simultaneously with the reaction rate in modulated‐temperature DSC (MTDSC). To predict the effect of T_cure and the NH/epoxy molar mixing ratio (r) on the reaction rate in chemically controlled conditions, a mechanistic approach was used based on the nonreversing heat flow and heat capacity MTDSC signals, in which the reaction steps of primary (E_1OH = 44 kJ mol^?1) and secondary amine (E_2OH = 48 kJ mol^?1) with the epoxy–hydroxyl complex predominating. The diffusion factor DF as defined by the Rabinowitch approach expresses whether the chemical reaction rate or the diffusion rate determines the overall reaction rate. A model based on the free volume theory together with an Arrhenius temperature dependency was used to calculate the diffusion rate constant in DF as a function of conversion (x) and T_cure. The relation between x, r, and T_g, needed in this model, can be predicted with the Couchman equation. An experimental approximation for DF is the mobility factor DF* obtained from the heat capacity signal at a modulation frequency of 1/60 Hz, normalized for the effect of the reaction heat capacity in the liquid state and the change in C_p in the glassy region with x and T_cure. In this way, an optimized set of diffusion parameters was obtained that, together with the optimized kinetic parameters set, can predict the reaction rate for different cure schedules and for stoichiometric and off‐stoichiometric mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2814–2833, 2004     

Augment low-field intra-operative MRI with preoperative MRI using a hybrid non-rigid registration method

Background

Preoperatively acquired diffusion tensor image (DTI) and blood oxygen level dependent (BOLD) have been proved to be effective in providing more anatomical and functional information; however, the brain deformation induced by brain shift and tumor resection severely impairs the correspondence between the image space and the patient space in image-guided neurosurgery.

Method

To address the brain deformation, we developed a hybrid non-rigid registration method to register high-field preoperative MRI with low-field intra-operative MRI in order to recover the deformation induced by brain shift and tumor resection. The registered DTI and BOLD are fused with low-field intra-operative MRI for image-guided neurosurgery.

Results

The proposed hybrid registration method was evaluated by comparing the landmarks predicted by the hybrid registration method with the landmarks identified in the low-field intra-operative MRI for 10 patients. The prediction error of the hybrid method is 1.92 ± 0.54 mm, and the compensation accuracy is 74.3 ± 5.0%. Compared to the landmarks far from the resection region, those near the resection region demonstrated a higher compensation accuracy (P-value = .003) although these landmarks had larger initial displacements.

Conclusions

The proposed hybrid registration method is able to bring preoperatively acquired BOLD and DTI into the operating room and compensate for the deformation to augment low-field intra-operative MRI with rich anatomical and functional information.     

Curing process of powdered phenol–formaldehyde resol resins and the role of water in the curing systems

The curing behavior of two kinds of commercial powdered resol phenolic resins was studied by differential scanning calorimetry. Liquid‐state ¹³C‐NMR spectroscopy was used to aid in understanding the curing behavior by detecting the structure of powdered resins. The reaction mechanism was interpreted with the dependency of activation energy on the degree of conversion. The results indicate that there are differences in the curing mechanism between core and face phenolic resins. The curing process of core resin was faster than that of face resin at the same reaction temperature. The water added in the curing system played an important role of plasticizer or diluent according to different curing stages and water content. In the initial curing stage, water mainly diluted the system and retarded the curing reactions. However, at the higher degrees of conversion, water played the role of plasticizer to decrease the effect of diffusion on the curing reactions to make the curing reactions more complete. The excess water added in the curing system played the role of diluent at almost all stages during the curing process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1371–1378, 2003     

Studies on polyacrylates containing pendant ligand with carbonyl and hydroxyl functions and their divalent metal complexes

A series of monomers were prepared by reacting (meth)acryloyl chloride with 2,4‐dihydroxybenzophenone, 2,4‐dihydroxybenzaldehyde, and 2,4‐dihydroxyacetophenone, respectively. The monomers were polymerized in dimethylformamide (DMF) at 70°C using benzoyl peroxide as an initiator. Polymer–metal complexes were obtained from DMF solutions of polymers with an aqueous solution of metal ions. The polymers and polymer–metal complexes were characterized by elemental analysis and spectral studies. The IR spectra of these complexes suggest that the metals are coordinated through the oxygen of the carbonyl group and the oxygen of the phenolic–OH group. The electronic spectra, electron paramagnetic resonance (EPR) spectra, and magnetic moments of polychelates showed an octahedral and square planar structure for Ni(II) and Cu(II) complexes, respectively. X‐ray diffraction studies revealed that polychelates are highly crystalline. The thermal and electrical properties, catalytic activity, and structure–property relationships are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2083–2090, 2003     

NMR imaging and differential scanning calorimetry study on drying of pine,birch, and reed pulps and their mixtures

Drying, water fractions, and water distribution were investigated for pine, birch, and reed pulps and pine–birch, pine–reed, and pine–birch–reed pulp mixtures. Gravimetrically determined drying times showed that the drying rates of the pulps decreased at two to four inflection points. Characterizations of the dried pulps by differential scanning calorimetry (DSC) showed a faster removal of free water than freezing and nonfreezing bound waters; all decreased simultaneously, however. DSC also revealed the critical water contents at which the free water and freezing bound water disappeared. The gravimetrically determined inflection points of the drying curves corresponded with the critical points determined by DSC. NMR line widths and images produced by ¹H‐NMR imaging revealed the nature and regions of the pulp drying. The constant growth rate of the NMR line widths with decreasing water content appeared to change at two inflection points, which fell approximately in the same water content regions as the inflection points of the drying curves. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 937–945, 2006     

Properties and crystallization kinetics of poly(ether ether ketone)‐co‐poly(ether ether ketone ketone) block copolymers

A series of block copolymers composed of poly(ether ether ketone) (PEEK) and poly(ether ether ketone ketone) (PEEKK) components were prepared from their corresponding oligomers via a nucleophlilic aromatic substitution reaction. Various properties of the copolymers were investigated with differential scanning calorimetry (DSC) and a tensile testing machine. The results show that the copolymers exhibited no phase separation and that the relationship between the glass‐transition temperature (T_g) and the compositions of the copolymers approximately followed the formula T_g = T_g1X₁ + T_g2X₂, where T_g1 and T_g2 are the glass‐transition‐temperature values of PEEK and PEEKK, respectively, and X₁ and X₂ are the corresponding molar fractions of the PEEK and PEEKK segments in the copolymers, respectively. These copolymers showed good tensile properties. The crystallization kinetics of the copolymers were studied. The Avrami equation was used to describe the isothermal crystallization process. The nonisothermal crystallization was described by modified Avrami analysis by Jeziorny and by a combination of the Avrami and Ozawa equations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1652–1658, 2005     

自适应混合多目标分布估计进化算法

针对多目标分布估计算法全局收敛性较弱的缺陷,提出了一种自适应混合多目标分布估计进化算法。其基本思想是:在多目标分布估计算法中引入全局收敛性较强的差分进化算法,当函数变化率较大时,用分布估计算法产生新种群;当函数变化率较小即算法可能陷入局部收敛时,用差分进化算法产生新种群。理论分析和数值实验结果表明,这种混合算法不仅具有良好的全局收敛性,而且解的分布性和均匀性较没有考虑目标函数变化率的混合多目标分布估计算法也有了一定程度的提高。     

钒钼酸铵分光光度法快速测定磷酸二铵中有效五氧化二磷

为了快速测定磷铵中P2O5含量,将0.1mol/LEDTA预热至80±2℃作为DAP有效P2O5的提取液,提取时间25min以上。鉴于正磷酸根在酸性介质中与钼酸盐及偏钒酸盐生成稳定的黄色化合物,在400nm波长下,利用示差法测定P2O5仅需50～55min。该方法的相对标准偏差(RSD)为0.13%～0.28%,回收率99.1%～101.1%,精密度和准确度好。