Keggin结构含钒混配型杂多酸盐及其杂多蓝的极谱和热谱

本文利用极谱和循环伏安的方法研究了杂多酸盐 K3 H2 [Si V Mo2 W9O4 0 ]· 10 H2 O及其一电子杂多蓝 K4 H2 [Si V Mo2 W9O4 0 ]· 12 H2 O和杂多酸盐 K4 H3 [Si V3 W9O4 0 ]· 13H2 O及其两电子杂多蓝 K4 H5[Si V2 V W9O4 0 ]· 11H2 O的氧化还原性质 ,利用 TG- DTA曲线分析了这 4种物质的热稳定性。结果表明杂多酸盐被还原为杂多蓝后 ,氧化能力有所降低 ,但热稳定性增加。     

一组Dawson型多金属氧酸盐和相应的有机-无机杂多化合物的超快非线性光学响应

通过时间分辨率为115fs的超快光克尔方法测量了多金属氧酸盐K8[P2Mo4W13M(H2O)O61] (M=Mn, Co, Ni, Cu, Zn)和相应的有机-无机杂多化合物(C19H25N2)7K3[P2Mo4W13MO62]在830nm处的三阶非线性光学性质。多金属氧酸盐阴离子和相应的杂多化合物都表现出很大的三阶非线性,其中M=Cu的取代物的非线性系数要比其他小一个数量级。通过比较有机-无机杂多化合物和生成前者的反应物的值,发现杂多化合物中的电荷转移效应极大的增强了三阶非线性光学性能。     

Dawson结构磷钨钒杂多酸有机铵盐的合成及光谱研究

以偏钒酸铵、磷酸二氢钠和钨酸钠为原料,调节溶液的pH值为4,控制反应时间为10 h,合成了三钒取代的Dawson结构磷钨钒杂多酸,然后以化学反应计量的5倍量加入抗衡离子K+,制备了母体杂多酸盐K9P2W15V3O62·41H2O。在不断的搅拌下,将母体杂多酸盐的酸性溶液缓慢滴加到十六烷基三甲基溴化铵溶液中,合成了目标化合物磷钨钒杂多酸有机铵盐(C19H42N)6H3[P2W15V3O62]。经元素分析、红外光谱、X射线粉末衍射、差热-热重等手段进行了表征,表明目标化合物仍保持Dawson结构,为未见文献报道的杂多化合物。     

三元杂多阴离子层状化合物的合成、表征及催化活性

用离子交换法合成了具有Keggin结构的三元杂多阴离子层状化合物LDH-K8[MnCu(H2O)W11O39],LDH-K8[MnFe(H2O)W11O39],LDH-K8[MnCo(H2O)W11O39]和LDH-K8[MnZn(H2O)W11O39],并用XRD、IR、UV对其进行了表征。结果表明:杂多阴离子进入水滑石层间后,仍保留了其Keggin结构。利用层状化合物催化合成乙酸正丁酯考察其催化活性,结果表明:层状化合物在酯化反应中显示优良的催化性能。     

两种手性超分子螺旋链化合物的结构、VCD和荧光分析

采用非手性物质合成了配位聚合物[C10H18CuN2O9S]n（1）和[C10H14CdN2O7S]n（2）。通过元素分析,红外光谱（IR）,热稳定性分析,荧光光谱,X射线粉末衍射（XRD）,X射线单晶衍射对其进行了分析。结构分析表明,1和2分别属于手性空间群P 65和P 6122,均在c轴方向上通过氢键形成一维超分子螺旋链。振动圆二色谱（VCD）表明两种配位聚合物都非外消旋的,分析了螺旋结构对VCD光谱影响,并对2的VCD光谱进行了理论计算,计算结果与实验相符,表明化合物手性可能来自一维超分子螺旋链。二者的固体荧光光谱分析表明：1在468nm处的宽峰为金属与配体的相互作用引起的;2在325—450nm处荧光主要由配体产生,配体与Cd的配位作用形成的刚性平面增强了荧光的强度。     

A2Ca[B4O5(OH)4]2·8H2O(A＝Rb, Cs)合成、 FTIR光谱及激光拉曼光谱研究

采用Rb2 CO3 ,Cs2 CO3 ,H3 BO3 和CaCl2 合成了新的硼氧酸盐复盐Rb2 Ca[B4O5(OH) 4 ]2 ·8H2 O和Cs2 Ca[B4O5(OH) 4 ]2 ·8H2 O ,通过化学分析和热分析等确定了化学物的组成。给出了两种化合物的FTIR光谱和Ra man光谱 ,分析了各种谱线的归属。     

取代基效应对二芳基硝酮CH=N(O)桥基1H NMR化学位移的影响

合成一系列取代二芳基硝酮XArCH=N（O）ArY化合物,测定其核磁共振氢谱（¹H NMR）,指认出桥基CH=N（O）上质子的化学位移δH[CH=N（O）],定量研究取代基效应对δH[CH=N（O）]的影响.得到一个4参数定量方程,标准偏差（S）为0.020,较好地表达了δH[CH=N（O）]的变化规律.结果表明,该类化合物的δH[CH=N（O）]主要受4个因素影响：X基团的场/诱导效应[σ_F（X）];Y基团的共轭效应[σ_R（X）];基团X和Y之间的特殊交叉作用（Δσ²）;以及基团X和O^-之间的特殊交叉作用[Δσ²_（X-O^-）].其中,Δσ²_（X-O^-）对δ_{H[CH=N（O）]}变化的贡献超过70%.通过δH[CH=N（O）]与二芳基希夫碱XArCH=NArY桥基CH=N上质子化学位移的δH（CH=N）比较发现,这两类化合物桥基上质子的化学位移之间没有良好的线性关系.因而,在应用NMR谱图解析有机化合物分子结构时,不能简单地用δH（CH=N）的变化去类比δ_{H[CH=N（O）]}的变化.     

若干具有[(PO4)4MoⅤ6O15]12-簇骼的化合物的光谱研究

用FTIR, NIR FT-Raman, UV-Vis DRS和荧光光谱等对五个新型具有[(PO4)4MoⅤ6O15]12-阴离子簇的化合物: Na·(H4TETA)3·(H3O)5·{Zn[(HPO4)2(PO4)2Mo6O15]2} (2), (H2 en)7·(H3O)4·{Cu[(HPO4)2(PO4)2Mo6O15]2}·H2O (3), (H3DETA)2·(H3O)3·{Co0.5[(HPO4)2(PO4)2Mo6O15]}·H2O (4), [Co(H3TETA)]2{Co0.5[(HPO4)(PO4)3Mo6O15]}·3.5H2O (5)和(H3DETA)·(H3O)4·{Co1.5[(HPO4)2(PO4)2Mo6O15]}·0.5H2O (6), 进行研究, 并探讨其结构和性能的关系. 这些化合物具有{M[(PO4)4Mo6 O15]2}二聚体单元, 化合物2～4的二聚体间通过与有机分子和水分子的氢键形成三维网状结构; 化合物5和6的{Co[(PO4)4Mo6O15]2}二聚体间是分别通过 [CoH3TEATA]基团和CoO4四面体组成网状结构. 磷钼酸盐的特征振动频率和这些化合物的结构相关; 化合物的三个UV-Vis DRS特征谱带分别属于Od→Mo, Oμ→Mo 和O→M电荷转移; 观察到以240 nm激发, 在410 nm附近出现的由Oμ→Mo跃迁激发引起的较强的荧光发射谱带.     

若干具有[(PO_4)_4Mo_6~ⅤO_(15)]~(12-)簇骼的化合物的光谱研究

用FTIR ,NIRFT Raman ,UV VisDRS和荧光光谱等对五个新型具有 [(PO4) 4 MoⅤ6O15]12 -阴离子簇的化合物 :Na·(H4TETA) 3 ·(H3 O) 5·{Zn[(HPO4) 2 (PO4) 2 Mo6O15]2 } (2 ) ,(H2 en) 7·(H3 O) 4 ·{Cu[(HPO4) 2(PO4) 2 Mo6O15]2 }·H2 O (3) ,(H3 DETA) 2 ·(H3 O) 3 ·{Co0 5[(HPO4) 2 (PO4) 2 Mo6O15]}·H2 O (4) ,[Co(H3 TETA) ]2 {Co0 5[(HPO4) (PO4) 3 Mo6O15]}· 3 5H2 O (5 )和 (H3 DETA)· (H3 O ) 4 · {Co1 5[(HPO4) 2(PO4) 2 Mo6O15]}·0 5H2 O (6 ) ,进行研究 ,并探讨其结构和性能的关系。这些化合物具有 {M [(PO4) 4 Mo6O15]2 }二聚体单元 ,化合物 2～ 4的二聚体间通过与有机分子和水分子的氢键形成三维网状结构 ;化合物 5和 6的 {Co[(PO4) 4 Mo6O15]2 }二聚体间是分别通过 [CoH3 TEATA]基团和CoO4四面体组成网状结构。磷钼酸盐的特征振动频率和这些化合物的结构相关 ;化合物的三个UV VisDRS特征谱带分别属于Od→Mo,Oμ→Mo和O→M电荷转移 ;观察到以 2 4 0nm激发 ,在 4 10nm附近出现的由Oμ→Mo跃迁激发引起的较强的荧光发射谱带。     

11-钨锌三元杂多阴离子层状化合物的合成、表征及催化活性

用离子交换法将具有K egg in结构11-钨锌三元杂多化合物K8[M ZnW11（H2O）O39]（M=Co2＋、N i2＋、Cu2＋、Cd2＋）嵌入到Zn2A l类水滑石中,得到层状化合物：Zn2A l-[M ZnW11（H2O）O39]（M=Co2＋、N i2＋、Cu2＋、Cd2＋）,并用XRD、IR、UV对其进行了表征。结果表明,杂多阴离子进入水滑石层间后,仍保留了其K egg in结构。利用层状化合物催化合成乙酸正丁酯考察其催化活性,结果表明,层状化合物在酯化反应中显示优良的催化性能。     

Solid polymer electrolytes based on poly(lithium carboxylate) salts

The ionic conductivity, lithium ion transference number, electrochemical stability, and thermal property of solid polymer electrolytes composed of poly(ethylene oxide) (PEO) and poly(lithium carboxylate)s, (poly(lithium acrylate) (Poly(Li-A)) or poly(lithium fumarate) (Poly(Li-F)), with and without BF₃·OEt₂ were investigated. The ionic conductivities of all solid polymer electrolytes were enhanced by one to two orders of magnitude with addition of BF₃·OEt₂ because the dissociation of lithium ion and carboxylate anion was promoted by the complexation with BF₃. The lithium ion transference number in the solid polymer electrolytes based on poly(lithium carboxylate)s showed relatively high values of 0.41–0.70, due to the suppression of the transport of counter anion by the use of a polymeric anion. The solid polymer electrolytes with addition of BF₃·OEt₂ showed good electrochemical stability.     

Novel Poly(benzoxazole-etherimide) Copolymer for Two-Layer Flexible Copper-Clad Laminate

A new random co-polyimide (co-PI), poly(benzoxazole-etherimide), was prepared via the poly(amic acid) from the reaction of 5-amino-2-(4-aminobenzene)-1,3-benzoxazole (BOA) and 4,4′-oxydianiline (ODA) with 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) at a diamine molar ratio of 6:4. The BOA-type and ODA-type homo-PIs were also prepared for comparison. The aggregation structure and properties of the PI films were analyzed. The co-PI film showed a good balance in thermal properties, tensile strength, film toughness, and water absorption. The two-layer flexible copper-clad laminates made from these PIs were produced by coating poly(amic acid) solutions onto copper foils and then imidizing thermally. The adhesion properties and relative thermodimensional stability of the laminates were evaluated. The laminate based on the co-PI had higher relative thermodimensional stability as well as better adhesion property than those based on the two homo-PIs, which is due to the improvement in both the bonding strength of PI/copper at the interface and the cohesive strength of the co-PI itself in the boundary layer near the interface.     

Graphene oxide doped poly(vinylidene fluoride-co-hexafluoropropylene) gel electrolyte for lithium ion battery

Gel poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer electrolytes doped with graphene oxide (GO) (GO/PVDF-HFP) were designed and fabricated through a phrase inversion method and followed by LiPF₆ solution uptake. It was demonstrated that the as-prepared GO/PVDF-HFP polymer electrolytes have uniform porous morphologies, and their crystalline state, thermal stability, interfacial resistance, and electrolyte uptake and retention capabilities can be tuned by varying the GO contents. Further, it was found that the GO can prominently enhance the ionic conductivity of the GO/PVDF-HFP polymer electrolyte. The electrochemical property measurements show that the lithium ion batteries using as-prepared GO/PVDF-HFP polymer electrolytes afford admirable charge/discharge rate and cycle stability.     

Temperature dependence of the stress transfer for thermal resistance polymer composites by X-ray diffraction

Temperature dependence of the stress transfer from the matrix resin to the incorporated fiber has been measured for poly(p-phenylene benzobisoxazole) (PBO) fiber/bismaleimide (BMI) resin composite by a novel X-ray diffraction method. At 120°C, stress transfer and tensile strength of the PBO/BMI composite are superior to that of the PBO/epoxy composite, due to the excellent thermal resistance and good mechanical property of BMI resins. The PBO/BMI composite possesses good adhesion and excellent mechanical properties at high temperature, which are suitable for thermal resistance applications.     

Arrayed waveguide grating multiplexer with high thermal stability on silicon

In this paper, certain important parameters are optimized for a polymer/Si arrayed waveguide grating (AWG) multiplexer by using grating theory. A 32-channel multiplexer is designed and fabricated using newly synthesized fluorinated poly (ether ether ketone) with a high thermal stability. The measured wavelength channel spacing is 0.796 nm, and center wavelength and 3-dB bandwidth are 1548 nm and 0.3 nm, respectively.     

气泡型铷原子频标光谱灯优化设计

铷光谱灯作为被动型铷原子频标的重要部件之一,对铷频标整机性能的影响很大. 为了满足高稳定性以及在真空、高温等特殊环境下正常工作的要求,从谱灯振荡电路稳定性、电屏蔽、热设计等方面着手,设计出一套新结构的谱灯. 文中报道了该谱灯的设计思路和初步测试结果.      

Effect of Substituents and Dopants on the Structure–Property Relationship of Poly(Aniline)—A Comparative Study

Effects of substituents and dopants on the structure–property relationships of poly(aniline) (PANI)-type homopolymers are analyzed. The gravimetric method was used for the estimation of rate of polymerization (R_p). FTIR spectroscopy was used for the calculation of relative intensities (RI) of benzenoid (RI_[B/CH]), quinonoid (RI_[Q/CH]), and their internal conversion (RI_[B/Q]). Thermogravimetric analysis (TGA) characterized the thermal stability of PANIs. A standard four probe method was employed for the conductivity measurements. The results are analyzed and critically compared.     

YBCO线圈在低温下的温度仿真分析

近几年,高温超导线材的制造技术已日趋成熟。作为第二代高温超导带材的代表,YBCO在低温下具有的优点使其在超导磁体领域的应用越来越突出。但是在高温超导磁体的运行中会因为受到扰动而失超。为了探讨这个问题,模拟了一个磁体在低温下(20K左右)有加热点扰动时的稳定性情况,即对YBCO线圈在低温下的工作情况进行了模拟仿真。文中根据实验设计的YBCO单饼线圈参数,利用热传导方程和基本电路方程,采用有限元计算方法,模拟出线圈内部的温度分布。分析仿真结果可以为后续实验设计提供参考。     

Proton conducting composite membranes comprising sulfonated Poly(1,4-phenylene sulfide) and zeolite for fuel cell

Sulfonated poly(1,4-phenylene sulfide; SPPS) was prepared from poly(1,4- phenylene sulfide) and fuming sulfuric acid by sulfonation process. Novel hybrid organic/inorganic composite polymer electrolyte membranes based on sulfonated poly(1,4-phenylene sulfide) membrane with varying concentrations of zeolite were synthesized. Fourier transform infrared spectroscopy implied the presence of a specific interaction between SPPS and zeolite particles. Upon increasing the zeolite concentration to 10 wt.%, the proton conductivity of composite membrane reduced from 0.075 to 0.02 S cm⁻¹ at room temperature which may be due to strong interaction between sulfonic group of SPPS and the zeolite particles. The water uptake of the composite membrane reduced from 255% to 150% with the increase of the zeolite concentration to 10 wt.%. The thermal stability analysis showed the enhancement of thermal stability of the composite membranes with increasing concentration of zeolite.