Ab initio modelling of crosslinking in polymers. A case of chains with furan rings

A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C₃ and C₄ atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions.     

Bipyridinophane‐containing conjugated polymers modulated with an intramolecular aromatic C?H/π interaction

Bipyridinophane–fluorene conjugated copolymers have been synthesized via Suzuki and Heck coupling reactions from 5,8‐dibromo‐2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane and suitable fluorene precursors. Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P7 ) exhibits large absorption and emission redshifts of 20 and 34 nm, respectively, with respect to its planar reference polymer Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐1,4‐(2,5‐dimethylbenzene)] ( P11 ), which bears the same polymer backbone as P7 . These spectral shifts originate from intramolecular aromatic C? H/π interactions, which are evidenced by ultraviolet–visible and ¹H NMR spectra as well as X‐ray single‐crystal structural analysis. However, the effect of the intramolecular aromatic C? H/π interactions on the spectral shift in poly[9,9‐dihexylfluorene‐2,7‐yleneethynylene‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P10 ) is much weaker. Most interestingly, the quenching behaviors of these two conjugated polymers are largely dependent on the polymer backbone. For example, the fluorescence of P7 is efficiently quenched by Cu²⁺, Co²⁺, Ni²⁺, Zn²⁺, Mn²⁺, and Ag⁺ ions. In contrast, only Cu²⁺, Co²⁺, and Ni²⁺ ions can partially quench the fluorescence of P10 , but much less efficiently than the fluorescence of P7 . The static Stern–Volmer quenching constants of Cu²⁺, Co²⁺, and Ni²⁺ ions toward P7 are of the order of 10⁶ M^?1, being 1300, 2500, and 37,300 times larger than those of P10 , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4154–4164, 2006     

光学三维成像实验系统

建立光学投影层析三维成像系统,该系统包括光学成像、图像采集、断层重建及三维显示,重建算法为滤波反投影算法.实验结果表明:利用该系统得到的重建图像与样品的形状吻合,重建结果边缘清晰,伪迹较小.     

不同方法制备的CO2-3替换磷灰石固溶体晶体化学的FTIR研究

采用不同方法制备了CO2-3替换的磷灰石固溶体,利用FTIR结合XRD对其进行了晶体化学研究,结果表明均相沉淀法制备的碳羟磷灰石(CHAP)属B型替换且替换方式是[CO3·OH]四面体替换[PO4]四面体;固相离子交换法制备的CHAP属A型替换且替换方式是[CO3]三角形配位体替换通道位置的OH-;固相反应法制备的碳氟磷灰石(CFAP)属B型替换,其替换方式是[CO3·F]四面体替换[PO4]四面体;sol-gel法制备的CHAP属AB混合型替换,其Ψ3分裂为Ψ3-1,Ψ3F,Ψ3-4.高斯函数法拟合表明Ψ3F峰是A型替换的Ψ3-2与B型替换的Ψ3-3的叠合.当WCO2-3＜3.34%时,随CO2-3含量增加,A型替换量增大,且当WCO2-3=3.34%时达最大值,当3.34%＜WCO2-3＜7.52%时,随CO2-3含量增加,B型替换量增大,且当WCO2-3= 7.52%时亦到饱和.     

金刚石窗口冷却Yb3+∶YAG DPSSL设计

针对高功率二极管重复率抽运的V型非稳腔Yb3+∶YAG激光头，提出了利用金刚石窗口冷却和直接水冷相结合的复合冷却设计.在YAG片的抽运面进行直接水冷，同时在激光提取面利用金刚石窗口冷却介质.金刚石优异的导热性能不仅能够有效地冷却激光介质，还能消除横向的温度梯度，解决了高功率激光器冷却和高功率抽运的矛盾.模拟结果表明对掺杂10 at %厚度为1.6 mm的Yb3+∶YAG片在抽运功率密度为20 kW/cm2，重复频率为10 Hz的条件下，要将最高温度控制在可接受的范围内（比如320 K），周围冷却水的对流换热系数约为4000 W/m2K.     

Gd3+对Ca0.8Zn0.2TiO3:Pr3+红色发光材料的敏化作用

采用溶胶-凝胶法在较低温度下合成了红色发光材料Ca0.8Zn0.2TiO3:0.002Pr3 ,xGd3 .金属离子预先溶解含有柠檬酸的乙二醇溶液中.XRD表明在800℃灼烧2h形成了钛酸盐的晶体.荧光检测结果表明所合成样品的特征激发峰为330nm、特征发射峰为614nm,分别对应于O(2p)→Ti(3d)带间跃迁和Pr3 的1D2→3H4的特征发射.样品的发光强度随x的不同而不同,发光强度增强了29%-69%.当x＝0.0005时,即nPr3 :nGd3 ＝4∶1时样品的红色发光强度最强,发光强度增强了69%.     

激光穿透焊的三维数值模拟

本文对激光穿透焊进行了三维数值模拟，除考虑焊接速度影响外，还研究了Ｍａｒａｎｇｏｎｉ对流对熔池流动与传热的影响。将三维数值模拟结果与相应的二维模拟结果进行了比较，结果表明，Ｍａｒａｎｇｏｎｉ对流对熔池的形成有很大的影响，因此不可忽略。本文还给出了估计激光穿透焊中蒸气孔尺寸与焊接热效率的方法。     

Design of polarization retarder suitable for nonlinear optical systems

We present a design technique of retarders suitable for nonlinear optical systems. A thin sample of LiNbO₃ crystal is utilized as a retarder for wide-ranging applications. Analysis shows that the same crystal can be used for single-wave or two-wave retardations, changing the orientation of the crystal only. As an application, the retarder is used to polarize two waves orthogonal, as necessary for difference frequency mixing in an AgGaSe₂ crystal.     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

利用莫尔条纹的准正弦特性的三维轮廓术

分析了两个矩形光栅迭合产生的莫尔条纹的光强分布特性，通过选择适当的光栅参数，可得到一个近似的正弦分划板，并把它用于三维面形测量中，实验结果表明，这种方法简单，易于自动处理，有广泛的实用价值。