液态金属铝的热历史对凝固微结构的影响

用分子动力学模拟研究了液态金属Al 系统的热历史对凝固微结构的影响.发现在同一系统中、不同的热历史条件下， 1551 键型和与1551键型相关的二十面体结构(12 0 12 0)在微结构的转变过程中均起着非常重要的作用. 特别有意义的是, 在每个温度的等温运行中能够重复出现的二十面体的数目不随温度的降低而增加, 并有一个极大值.该极大值点正好与其玻璃转变温度Tg相对应, 在不同的热历史条件下极大值的位置是能够移动的.结果还显示出, 热历史条件对微结构转变有严重影响, 且其作用主要是在玻璃转变温度点Tg以后才显示出来. 这就为我们理解和控制凝固过程中的微结构转变提供了一条新途径.     

钠硼硅酸盐玻璃分相微结构的NMR研究

采用 ²⁹Si、 ¹¹B MAS NMR研究了组成点位于Na₂O-B₂O₃-SiO₂三元体系玻璃分相区内的玻璃，探讨组成点不同及处理温度不同产生的分相微结构的差异，以便从微结构角度阐明分相的机制。结果表明：在相同温度下位于反常线上的组成点不混溶程度最大。而当组成点固定、分相温度愈低，［BO₃］向［BO₄］的转化率愈大。研究结果提供了     

聚丙烯催化合金结构表征

用IR、DSC、NMR分析了聚丙烯催化合金中乙丙共聚物的微结构 ,发现在一定条件下合成的乙丙共聚物主要由两部分组成 :无规乙丙共聚物和各种不同序列长度的乙丙嵌段物组成 .加上丙烯均聚物 ,聚丙烯催化合金是一种具有多分散性结构的混合物 .这种特殊的结构是聚丙烯催化合金具有高抗冲性的主要原因     

固体核磁共振研究进展——邓风研究员及其团队专访

正与X射线衍射相比,固体核磁共振(NMR)作为一种重要的谱学技术,它对体系中的近程有序变化更为敏感,非常适合用于研究各类非晶固体材料的微观结构和动力学行为,能够提供原子分子水平的结构信息。固体NMR已被广泛应用于多相催化、聚合物、玻璃、锂电池、纳米材料、药物和膜蛋白等诸多     

多光子光刻用的杯[4]芳烃分子玻璃正性光刻胶

分子玻璃材料和多光子光刻技术分别是近年来光刻胶和光刻技术领域的研究热点.本文对分子玻璃正性光刻胶在多光子光刻中的应用进行了探索,设计合成了叔丁氧基羰基保护的杯[4]芳烃衍生物分子玻璃材料,将其作为主体材料与光生酸剂三氟甲磺酸三苯锍鎓盐进行复配,制备了分子玻璃正性光刻胶,探讨并优化了光刻胶的成分配比及其在紫外光曝光下的显影工艺.利用780nm波长飞秒激光对所制备的分子玻璃正性光刻胶进行了多光子光刻特性的评价,实验得到了最低线宽180nm的线条和复杂的二维微结构图形,结果表明杯[4]芳烃衍生物分子玻璃正性光刻胶有望应用于多光子光刻技术.     

三亚甲基碳酸酯和己内酯生物可降解共聚物序列结构的二维核磁分析

以辛酸亚锡[Sn(Oct)2]为催化剂、乙二醇为引发剂,通过本体开环共聚,合成了己内酯(CAP)与三亚甲基碳酸酯(TMC)的共聚物。采用1H、13C核磁共振及同核二维相关谱(gCOSY)、13C-1H异核相关谱(gHSQC)和13C-1H异核远程相关谱(gHMBC)等二维核磁共振(2D NMR)技术,对所合成的聚合物进行了序列微结构表征,找出了聚合物分子链中序列连接方式,并完成了1H和13C NMR谱带的归属。     

2-乙烯基吡啶与甲基丙烯酸甲酯共聚物的高分辨^1HNMR研究

本文根据自由基引发聚合的2-乙烯基吡啶-甲基丙烯酸甲酯共聚物的~1H NMR谱,定量地研究了共聚物中的微结构单元及其组成.对分别以2-乙烯基吡啶和甲基丙烯酸甲酯为中心的三元组分分布,都做了定量测定.确定了该共聚体系属于一级Markov链模型和单体竞聚率γ_v=O.64,γ_m=O.31.与理论上的计算结果吻合良好.     

掺杂CuInS2纳米晶玻璃的三阶非线性光学性质

采用溶胶-凝胶法结合气氛控制制备了CuInS2纳米晶玻璃. 利用X射线粉末衍射仪(XRD)和透射电子显微镜(TEM)对CuInS2纳米晶在玻璃中的形貌和微结构进行了表征, 并利用飞秒Z扫描技术对该玻璃的三阶非线性光学性质进行了研究. 结果表明, 在钠硼硅玻璃中形成了尺寸分布为10 nm左右的均一的CuInS2四方晶系纳米晶. 该玻璃体现出优良的三阶非线性光学性能, 其三阶非线性光学折射率γ、吸收系数β和极化率χ(3)分别为8.57×10-16 m2/W, 3.74×10-8 m/W和1.95×10-17 m2/V2.     

In2S3量子点玻璃的制备及其三阶非线性光学性质

本文利用溶胶-凝胶法结合气氛控制合成了含In2S3量子点玻璃。利用X射线粉末衍射仪(XRD),X射线光电子能谱(XPS),透射电子显微镜(TEM),X射线能量色散谱(EDX),高分辨透射电子显微镜(HRTEM)以及选区电子衍射(SAED)对In2S3量子点在玻璃中的微结构进行了表征,同时,利用飞秒Z-scan技术详细地研究了该玻璃在800 nm处的三阶非线性光学性质。结果表明,尺寸分布在12～20 nm之间的In2S3四方晶系纳米晶已经在玻璃中形成,并且,该玻璃展示出了优异的三阶非线性光学性能,其三阶非线性光学折射率γ、吸收系数β和和极化率χ(3)分别为-2.04×10-18m2·W-1,8.26×10-12m·W-1,和1.61×10-20m2·V-2。     

固体核磁共振研究碱土金属磷硅酸盐玻璃的六配位硅结构（英文）

磷酸盐玻璃在光学领域有广泛的应用,然而因为简单的磷酸盐玻璃的化学稳定性和热机械性能较差,已经难以满足日益发展的激光装置的高性能要求。在磷酸盐玻璃中加入少量的硅可以形成六配位的硅网络体并且极大的改善这些性能。因此研究这种磷硅酸盐玻璃的结构细节有重要的意义。但是由于玻璃结构缺乏长程有序,其结构研究比较复杂。现代固体核磁共振(NMR)技术能够从原子尺度对无序状态的物质局域结构进行解析,是一种强大的用来研究玻璃结构的技术手段。本文的目的是探究碱土金属对磷硅酸盐玻璃中六配位硅结构的影响。我们采用传统的熔融-冷却法制备了(2MO-3P_2O_5)_((1-x))·(SiO_2)_x(M=Ca,Sr,Ba)体系的磷硅酸盐玻璃。并且运用先进的固体核磁共振技术和拉曼光谱对此磷硅酸盐玻璃结构进行了表征。~(31)P和~(29)Si MAS NMR表明其网络结构由磷氧四面体P~((2))和P~((3))与四配位和六配位的硅氧多面体相互连接构成,随着二氧化硅含量的增加六配位硅的比例呈现减少的趋势。类似地,在拉曼光谱的结构中和六配位硅相连的磷基团的峰也随着硅含量的增加而减弱。基于双量子相干和P-P同核间J耦合作用的重聚INADEQUATE实验证明了不同的磷氧四面体之间的连接情况,P~((2))和P~((3))两种结构单元在玻璃中是相对分离的,他们大多数都是与自身相连接。和之前报道的有关Na_2O-P_2O_5-SiO_2体系的玻璃相比较,不同的是,在Na_2O-P_2O_5-Si O_2玻璃中一个P~((3))结构单元最多有一个Si~((6))―O―P~((3))键,而对于本文的碱土金属磷硅酸盐玻璃一个P~((3))结构单元最多有0.4–0.7个Si~((6))―O―P~((3))键。说明碱土金属比碱金属对六配位硅的稳定作用更弱一些。这种结构与组成之间的关系对设计玻璃组成和性质能提供重要的依据,尤其在大型的激光装置中对磷酸盐玻璃基质的化学和热稳定性有着很高的要求,详细的结构信息能为通过改变组成来提高善玻璃性能搭建桥梁。     

The structure of phosphate and borosilicate glasses and their structural evolution at high temperatures as studied with solid state NMR spectroscopy: Phase separation,crystallisation and dynamic species exchange

In this contribution we present an in-depth study of the network structure of different phosphate based and borosilicate glasses and its evolution at high temperatures. Employing a range of advanced solid state NMR methodologies, complemented by the results of XPS, the structural motifs on short and intermediate length scales are identified. For the phosphate based glasses, at temperatures above the glass transition temperature T_g, structural relaxation processes and the devitrification of the glasses were monitored in situ employing MAS NMR spectroscopy and X-ray diffraction. Dynamic species exchange involving rapid P–O–P and P–O–Al bond breaking and reforming was observed employing in situ ²⁷Al and ³¹P MAS NMR spectroscopy and could be linked to viscous flow. For the borosilicate glasses, an atomic scale investigation of the phase separation processes was possible in a combined effort of ex situ NMR studies on glass samples with different thermal histories and in situ NMR studies using high temperature MAS NMR spectroscopy including ¹¹B MAS, ²⁹Si MAS and in situ ²⁹Si{¹¹B} REAPDOR NMR spectroscopy.     

NMR spectroscopy of bismuth fluoride glasses with alkali cations

Results of the ⁷Li, ¹⁹F, and ²³Na NMR studies of ionic mobility in bismuth fluoride glasses in the systems BiF₃-LiF and BiF₃-MF-ZrF₄ (M = Li, Na, K, Cs) are summarized. Analysis of the ⁷Li, ¹⁹F, and ²³Na NMR spectra made it possible to reveal changes in the nature of ion motions in the fluoride, lithium and sodium sublattices of glasses upon temperature variation and to determine their types. The temperature ranges were found where main types of ion motions in the tested glasses are represented by diffusion of lithium ions, reorientations of fluorine-containing groups constituting the glass network, and diffusion of fluorine ions. The role of alkali cations in the formation of ionic mobility in bismuth fluorozirconate glasses is considered.     

A magic-angle spinning 31P NMR investigation of crystalline and glassy inorganic phosphates

³¹NMR spectra of several inorganic phosphates have been examined both in the crystalline and the glassy states. The parameter (Z_eff/r)q clearly demarcates ortho-, pyro- and meta-phosphates in terms of the ³¹P chemical shifts. Based on such a diagram, inorganic phosphate glasses are found to consist essentially of metaphosphate units. NMR resonance of the glasses are generally much broader than those of crystalline phosphates.     

A 31P-NMR study of borophosphate glasses

It is shown that ³¹P nuclear magnetic resonance (NMR) spectroscopy with magic angle spinning (MAS) discriminates among different types of PO₄ units occurring in borophosphate glasses. The isotropic ³¹P chemical shift of the PO₄ increases by nearly 70 ppm in going from the “branching unit,” neutral and covalently bonded, to the “monomeric unit,” which carries a −3 nominal charge. By using both stationary and MAS ³¹P spectra, we also obtain the average values, and distribution widths, for chemical shift anisotropy and the asymmetry factor of PO₄ units occurring in vitreous borophosphates. Analysis of these NMR spectra provides detailed information about the short-range order in these glasses. It is also shown that the ³¹P-NMR-MAS technique may contribute significantly to phase separation and crystallization studies of phosphorus-containing glasses.     

NMR investigation of biodegradable polyesters for medical applications

Results of NMR studies of chain microstructure in polylactide, poly(lactide‐co‐ϵ‐caprolactone), poly(lactide‐co‐glycolide) and poly(glycolide‐ϵ‐caprolactone) are presented. The appropriate conditions of polymerization: temperature, solvents, type of initiators allows moulding of the structure of obtained polyesters. Statistical analysis of growing chains helps to identify in NMR spectra signals of the random and block segments of copolyester chains. Precise control of reaction conditions allows modification of chain structures by affecting rates of transesterification. Equations allowing for quantitative determination of the role of transesterification reactions on the basis of intensities of NMR resonance lines are given. Changes in the microstructure of macromolecular chains were determined using calculated values of transesterification coefficients, degree of randomness and values of average lengths of syndiotactic or isotactic blocks in lactide homopolymers or average lengths of comonomer units in copolymers.     

Proton conduction in nanopores of sol–gel-derived porous glasses and thin films

Nanoporous glasses and nanoporous thin films were prepared using sol–gel method, and proton conductivities in nanopores of sol–gel-derived porous glasses and thin films are overviewed in this paper. Proton motions inside nanopores were monitored by impedance and nuclear magnetic resonance (NMR) spectroscopies. The impedance data is correlated with the proton motion in bulk scale, whereas NMR data is correlated with that in nanometer scale, respectively. From the comparison of the activation energies obtained from impedance and NMR spectroscopies, percolation of proton conducting path and its relation to the amount of absorbed water molecules are shown. In the case of nanoporous thin films, directions of pores can be controlled by using cationic and non-ionic surfactants. Relationship between direction of pores and proton conductivity is discussed based on impedance test results.     

Organic glass-forming materials: 1,3,5-tris(naphthyl)benzene derivatives

The organic glass-forming materials 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2) and its partially deuterated analogue, 1,3-bis(1-naphthyl-d(7))-5-(2-naphthyl)benzene (2-d(14)), have been synthesized on a gram scale using Suzuki coupling reactions. Detailed spectroscopic studies afford complete NMR assignments (1H, 2H, 13C) for both compounds. Modest energy barriers for the interconversion of atropisomers (ca. 15 kcal/mol) result in a propensity for these materials to form supercooled liquids and glasses, rather than undergoing crystallization. The preparation of these materials enables detailed studies of physical properties of organic glasses and molecular diffusion in condensed phases.     

Direct crystallization of silicate–phosphate glasses of NaCaPO4–SiO2 system

The subject of the study was silicate–phosphate glasses of NaCaPO₄–SiO₂ system which are precursors of glass–crystalline materials. Glass–crystalline materials of NaCaPO₄–SiO₂ system obtained via crystallization of glasses belong to a group of the so-called bioactive materials. In order to obtain glass–crystalline materials with pre-established parameters, it is necessary to conduct crystallization of glasses at specific conditions. In order to design direct crystallization process properly, it is necessary to know the structure and microstructure of the glassy precursor. Microscopic investigation showed that liquation takes place in all the studied glasses. Based on DSC examinations, it has been found out that crystallization of the glasses of NaCaPO₄–SiO₂ system is a multistep process. The presence of several clearly separated exothermic peaks in DSC curves of investigated glasses makes it possible to crystallize only the separated phase with the matrix remaining amorphous or vice versa. Conducted detailed X-ray and spectroscopic studies of the materials obtained by heating in a gradient furnace (in the temperature specified on the basis of DSC) showed that separated phase and matrix crystallizes separately. Therefore, bioactive glass–crystalline materials can be obtained due to the existence of the phase separation phenomenon and pre-established sizes of the crystalline phase.     

Local structure of magnesium in silicate glasses: a 25Mg 3QMAS NMR study

We have reported the 25Mg triple-quantum magic-angle spinning (3QMAS) NMR spectra of silicate glasses. The two-dimensional spectra suggest that the magnesium ions in MgSiO3, CaMgSi2O6, Ca2MgSi2O7, Mg3Al2Si3O12, and Li2MgSi2O6 glasses are mainly in octahedral environments, although in Na2MgSi2O6, K2MgSi2O6, and K2MgSi5O12 glasses they form tetrahedral species. We discussed the coordination environments of Mg based on the field strength of competing Mg2+, Ca2+, Na+, K+, and Li+ cations, and convincingly demonstrated that there is a correlation between them. These results indicate that the two-dimensional NMR spectroscopy such as MQMAS technique is a very useful method to analyze the local environments of nonframework cations in noncrystalline solids.     

Structural Characterization of Non-Oxide Chalcogenide Glasses using Solid State NMR

In spite of the long-standing importance of non-oxide chalcogenide glasses in infrared optics and semiconductor technology, concepts describing the structural principles governing glass formation in these systems are just emerging. Most recently, modern quantitative solid state NMR techniques have offered new unique insights into the structural organization of these systems. In this review, we discuss the basic principles of various experimental approaches and their application to boron-silicon, -and phosphorus chalcogenide glasses.