The role of Al in C-S-H: NMR, XRD, and compositional results for precipitated samples

X-ray diffraction, compositional analysis, and ²⁹Si and ²⁷Al MAS NMR spectroscopy of Al-substituted tobermorite-type C-S-H made by precipitation from solution provide significant new insight into the structural mechanisms of Al-substitution in this important and complicated phase. Al occurs in 4-, 5-, and 6-coordination (Al[4], Al[5], and Al[6]) and plays multiple structural roles. Al[4] occurs on the bridging tetrahedra of the drierkette Al-silicate chains, and Al[5] and Al[6] occur in the interlayer and perhaps on particle surfaces. Al does not enter either the central Ca-O sheet or the pairing tetrahedra of the tobermorite-type layers. Al[4] occurs on three types of bridging sites, Q³ sites that bridge across the interlayer; Q² sites that are charge balanced by interlayer Ca⁺², Na⁺, or H⁺; and Q² sites that are most likely charge balanced by interlayer or surface Al[5] and Al[6] through Al[4]-O-Al[5,6] linkages. Although the data presented here are for relatively well-crystallized tobermorite-type C-S-H with C/S ratios ≤ 1.2, comparable spectral features for hydrated white cement pastes in previously published papers[30], [31] and [32] [M.D. Andersen, H.J. Jakobsen, J. Skibsted, Incorporation of aluminum in the calcium silicate hydrate (C-S-H) of hydrated Portland cements: a high-field ²⁷Al and ²⁹Si MAS NMR investigation Inorg. Chem. 42 (2003) 2280-2287; M.D. Andersen, H.J. Jakobsen, J. Skibsted, Characterization of white Portland cement hydration and the C-S-H structure in the presence of sodium aliminate by ²⁷Al and ²⁹Si MAS NMR spectroscopy, Cem. Concr. Res. 43 (2004) 857-868; M.D. Andersen, H. J. Jakobsen, J. Skibsted, A new aluminum-hydrate phase in hydrated Portland cements characterized by ²⁷Al and ²⁹Si MAS NMR spectroscopy, Cem. Concr. Res., submitted for publication.] indicate the presence of similar structural environments in the C-S-H of such pastes, and by implication OPC pastes.     

动态受限区域内的单纯型连续近邻链查询方法

受限区域内的单纯型连续近邻链查询在空间数据挖掘、数据的相似分析和推理、空间数据库等方面具有重要的作用。为了弥补已有方法的不足,详细研究了动态受限区域内的单纯型连续近邻链查询方法。基于计算几何中的Voronoi图给出了VOR_IN_CRSCNNC算法、VOR_EX_CRSCNNC算法和VOR_DE_CRSCNNC算法。进一步进行了实验比较和分析。理论研究和实验分析表明,所提出的算法在查询过程中减少了数据逐一筛选和判断的冗余计算,在处理空间数据量较大、初始受限区域数据量较多、受限区域形状较为复杂的单纯型连续近邻链查询方面具有较大的优势。     

Cure monitoring via different techniques: Isothermal cure of an epoxy-novolac molding compound

The isothermal cure of an epoxy-novolac molding compound was studied by means of Fourier-transform infrared spectroscopy (FTIR) and dielectrometry (DE). Results obtained were compared with previous differential scanning calorimetric (DSC) observations. The behavior of epoxide conversion (_FTIR) measured via FTIR was found similar to (but not exactly coinciding with) the extent of cure (_DSC) determined previously by means of DSC. As for the DE analysis, directly measurable properties such as permittivity () and loss factor () varied in a complicated manner during the course of cure, showing strong dependence on both temperature and frequency. Other dielectric parameters (such as ionic conductivity, relaxed permittivity, and characteristic relaxation time) previously suggested in the literature as suitable for cure monitoring purposes were found difficult to determine within the limited frequency range (10⁰ to 10⁴ Hz) here. With some arbitrariness, the relative drop in log (at 100 Hz) was taken as an index (_DE) for the extent of cure. It was observed that _DE behaves in a manner similar to _FTIR and _DSC Comments on the application of these three techniques in the characterization of thermosetting systems were given.     

QUANTITATIVE MEASUREMENT OF CHROMIUM'S ABILITY TO PROMOTE ADHESION

Using atomic force spectroscopy, we investigated the adhesion-promoting ability of chromium. An intermediate layer of chromium can overcome the low adhesion between metal films and silicon dioxide. For the first time, we quantitatively studied this experimentally well known fact. We compared the adhesion between chromium and different substrates such as gold, silver, mica, and silicon dioxide and, beyond that, the adhesion between silicon dioxide and the same substrates. To avoid additional effects due to water, we chose ethanol as a nonpolar solvent. Taking the interfacial energies of the surfaces with the liquid into account eliminates the direct influence of the fluid medium on the adhesion of the solid material. The results we obtained corroborate the experimental fact of higher adhesion of chromium with the chosen substrates, as well as substantiate the value of chromium as an adhesion promoter. The adhesion of chromium-coated probes on gold, silicon dioxide, and mica is higher than the adhesion of silicon dioxide probes on the same substrates.     

基于悬浮吸收层的热电堆红外探测器结构设计

在这项工作中,设计一种新颖的热电堆红外探测器结构。该检测器利用悬浮吸收层-热电堆双层结构来实现高性能,同时具有相对小的尺寸。该双层结构的实现是通过引入两个分离的牺牲层,分别包括热电堆下方的多晶硅膜和其上方的聚酰亚胺沉积实现。尺寸优化后的仿真结果表明,该红外探测器的探测率、响应率和响应时间分别可以达到2.85e8 cmHz （ 1/2） / W, 1800 V / W和6毫秒。此外,本文提出热电堆红外探测器的制造方法是高度兼容于标准的CMOS工艺,这就使其高产量和低成本的生产成为可能。     

Molecular orientation and relaxation in poly(butylene terephthalate)/polycarbonate blends

Rheo-optical Fourier-transform infrared (FTIR) spectroscopy is based on the simultaneous acquisition of stress-strain data and FTIR spectra on-line to the mechanical treatment of polymers and is frequently applied for the characterization of transient structural changes during deformation and stress-relaxation. In the present communication, this technique has been employed in order to investigate the distribution of molecular orientation and its relaxation in uniaxially drawn solution-cast films of semicrystalline partial miscible blends of poly(butylene terephthalate) (PBT) with polycarbonate (PC) containing 10, 30 and 50 wt% PC. The uniaxial deformation of these blend films having a PBT-crystallinity degree ranging from 31 to 12%, in unstretched blends, leads to a appreciable high segmental orientation for the crystalline PBT due to a structural transformation from lamellae to microfibrils. The formation of this fibrillar structure is attributed to non-reversibility of an extended phase with all-trans conformational sequence of the aliphatic segments of PBT, occurring during elongation. The rate of relaxation of this conformational transition, however, increases with increasing amorphous content in the blends. Also it is observed that even with increasing amorphous content in the PBT/PC blends the crystalline PBT shows significant orientation. In such cases, apart from the few lamellae which transform to microfibrils, it is suggested that a stress induced transformation of PBT chains in amorphous PBT-component to irreversible all-trans extended crystalline form also contributes to PBT crystalline orientation. In contrast with this high crystalline orientation, the amorphous PBT located in the interlamellar regions inside the PBT-spherulites show a lower orientation in blends as compared in pure PBT.On the other hand, an overall segmental orientation of PC chains in blends is of lower order which is attributed mainly to low stretching temperature compared to T_g of pure PC. The results are discussed in terms of the resulting spherulitic morphology and the temporary network formed by the elongated PBT and PC chains inside the interlamellar regions, in blends.     

Bulk and Interphase Effects in Aged Structural Joints

Although structural adhesives are becoming widespread in numerous applications, one important limitation at present is the long term behaviour of bonded assemblies under conditions of high humidity, especially at elevated temperatures. This study presents a comparison between bulk properties of a structural epoxy resin and its behaviour in a torsional joint consisting of a hollowed-out cylinder bonded to a plate—both substrates being in stainless steel. Exposure to ca. 100% relative humidity at 70°C leads to modification of the bulk properties of the polymer, notably reduction of its elastic modulus. Although this may explain some differences in behaviour of the torsional joint, premature failure is attributed to weaknesses in the interphase zone.

Auger Electron Spectroscopy (AES) has been employed to investigate both unbonded steel surfaces and fracture zones. Although prolonged exposure to water leads to a more extensive degree of (apparently) adhesive failure at the interface polymer/metal, AES has shown the presence of non-negligible quantities of carbon, attributed to residual polymer. Failure would seem to occur, at least partly, in a weak interphase of the polymer, near, but not at, the interface.

Various possible causes are evoked. For dry failure, residual polymer may be due to the topography of the metal surface and/or local modification of the adhesive during cure. In the case of aged joints, in addition there are potential effects due to swelling and differential stresses, secondary bond failure and molecular chain scission within the polymer, all provoked by the presence of water.     

Sensitive glasslike sol–gel materials suitable for environmental light sensors

New sol–gel based sensitive materials able to detect moderate doses of UV, Vis and near IR radiations have been designed, prepared and characterised. These glasslike detectors are respectively composed by four different sols of inorganic and hybrid organic–inorganic silica matrixes. The sols were prepared from alkoxide (TEOS) and alkylalkoxide (GLYMO) precursors with molar ratios 1:0, 1:1, 1:4 and 0:1, respectively. All the sols were doped with an organic photochromic dye (spiropyran). The detectors characterisation was carried out by means of exposures to natural light under different light intensities (100–3000 lx). The highest sensitivity against the light radiation was found for sols with molar ratio TEOS:GLYMO of 1:1. The time response of detectors is found at about 10 min and their life time is roughly 4 months at least. Moreover, the detectors show good optical reversibility. These sensitive glasslike materials have been designed to be applied for preservation of historical goods. They can detect and evaluate dangerous light doses for the proper conservation conditions of historical materials, which are sensitive or moderately sensitive against light radiation (<600 lx).     

一种快速、高效的红外摇控软件解码技术

通过分析红外遥控发射器发射码的特征,提出一种快速、高效的红外摇控软件解码技术。这种技术仅对发射码的功能码进行解析、存储、数据处理,降低对单片机存储空间的要求,降低了硬件成本,提高了系统的实时性。经实验测试,该方法能保证红外遥控信号的可靠接收。     

经验模态分解在电力绝缘气体SF6红外光谱去噪中的应用

经验模态分解(EMD)是以信号极值特征尺度为度量的时空滤波器,它充分保留了信号本身的非线性和非平稳特征,在信号去噪中具有较大的优势。本文以电力绝缘气体SF6为研究对象,在介绍E MD分解方法的基础上,首先对含噪的SF6光谱信号做EMD分解,得到各阶本征模态函数(IMF),然后对高频的IMF分量用阈值法进行处理,把经过阈值处理后的高频I MF分量与低频IMF分量叠加重构得到去噪后的信号。分析了在不同噪声水平上与小波阈值去噪方法的处理效果。实验结果表明EMD阈值去噪法有效地去除了噪声,较好地保留了光谱的细节信息,与小波阈值去噪方法相比较具有自适应的优势。