Calorimetric determination of enthalpies of lysozyme folding at a liquid-solid interface

Summary Two hydrated and aged cement pastes from India (NCB), w/c=0.4, of a similar chemical composition but of a different specific surface and different strength (OPC, C-33 and C-43), hydrated at w/c=0.4 for 1 month, were studied by XRD after 1 year and 5-6 year ageing on contact with air. They were tested by static heating (SH) in fresh state, and by DTA/DTG/TG, IR and mass spectrometry (MS), after ageing, presented elsewhere. The main XRD peaks of (i) portlandite were decreasing with T and disappearing about 450°C, (ii) calcite peak at room T was small and broad, it increased gradually, especially after portlandite disappearance; above 600°C it was lowered and it was lost above 700°C. Important variation in the d(001) of portlandite with ageing was observed, exceeding the standard value of d(001)=4.895 Å (72-0156). It was higher in the paste C-33 (4.925-4.936 Å), containing more carbonates, than in the paste C-43 (4.916-4.927 Å). Small variations only were found in the value of d(101), i.e. 2.627-2.635 Å (nominally 2.622 Å), whereas the d(104) of calcite could be used as internal standard and other calcium carbonates (vaterite and aragonite) showed a small variation only. The increase ind(hkl) with temperature was straight linear (in portlandite d(001)=0.095 Å, at 30-400°C) and the thermal expansion coefficient estimated thereform was high (4.75-4.95·10^-5 K^-1). Close to the T of decomposition the d/T became steeper. The thermal variation of d(104)=3.035 Å of calcite (d=0.015 Å at 30-400°C) was smaller than that ofd(101) of portlandite (d=0.025 Å at 30-400°C) and was similar in C-33 and C-43. The thermal expansion coefficient was 1.54 10^-5 K^-1, thus higher than the reported _a=0.65·10^-5 K^-1.     

Determination and imaging of binder remnants and aggregates in historic cement stone by Raman microscopy

We present to our knowledge the first application of Raman microscopic imaging to cementitious materials. This technique yielded the composition and phase distribution (spatial resolution ≈ 500 nm) in samples of cement stone taken from façade elements of four Swiss buildings covering the period of 1892–1924. Raman maps of Roman cement, a predecessor of modern Portland cement, reveal the chemical heterogeneity of clinker remnants consisting of various crystalline, polymorphic, and amorphous phases and visualize different crystal orientations. Our findings include the observation of the γ‐polymorph of Ca₂SiO₄ – previously, only detected in Portland cement – and Raman spectra of calcium aluminate (ferrite) interstitial phases in Roman cement showing significant differences to the corresponding phases in Portland cement clinker. Furthermore, calcite, vaterite, gypsum, and ettringite were identified in the rim of a nonhydrated residual nodule. Beyond binder remnants, aggregates in the form of spherical (≤500 µm diameter) slag and irregularly shaped pigment particles were analyzed. Here, we focused on the unambiguous identification of compounds in complex matrices by comparing sample spectra with database and own reference spectra. A Raman map collected on blast furnace slag in cement stone shows the spatial distribution of calcite, quartz glass and pyrite. Furthermore, several Fe‐containing, Si‐containing, and Pb‐containing phases were identified. The analysis of pigments partly confirmed and partly contradicted the bequeathed historic recipe of a cement stone façade. These results have direct implications in the field of conservation and restoration and generally demonstrate the potential of Raman imaging to provide deeper understanding of (historic) building materials. Copyright © 2013 John Wiley & Sons, Ltd.     

Elemental Analysis of Cement by Calibration-Free Laser Induced Breakdown Spectroscopy (CF-LIBS) and Comparison with Laser Ablation – Time-of-Flight – Mass Spectrometry (LA-TOF-MS), Energy Dispersive X-Ray Spectrometry (EDX), X-Ray Fluorescence Spectroscopy (XRF), and Proton Induced X-Ray Emission Spectrometry (PIXE)

The purpose of the present study is to determine the elemental composition of Pakistani cement brands using calibration-free laser induced breakdown spectroscopy (CF-LIBS) and to compare the obtained results with the other analytical techniques such as, laser ablation – time-of-flight – mass spectrometry (LA-TOF-MS), energy dispersive X-ray spectrometry (EDX), X-ray fluorescence spectroscopy (XRF) and proton induced X-ray emission spectrometry (PIXE). Compositional results reveal that all the cement brands are mainly composed of calcium, silicon, iron, aluminum, magnesium, potassium, sodium, titanium, lithium and strontium with varying concentrations. The compositions obtained by LIBS and LA-TOF-MS are in good agreement with results obtained by the other standard techniques and demonstrate the potential use of LIBS for the online monitoring of industrial cement production.     

Empirical dead‐time corrections for synchrotron sources

An experimental comparison of models for performing dead‐time corrections of photon‐counting detectors at synchrotron sources is presented. The performance of several detectors in the three operating modes of the Advanced Photon Source is systematically compared, with particular emphasis on asymmetric fill patterns. Several simple and well known correction formulas are evaluated. The results demonstrate the critical importance of detector speed and synchrotron fill pattern in selecting the proper dead‐time correction.     

Effect of thermal treatment of rice husk ash on surface properties of hydrated portland cement-rice husk ash pastes

Portland cement was mixed with rice husk ash (RHA) fired at 450, 700 and 1000C, in ratios of 5, 15 and 25% of RHA by mass. Cement-RHA pastes were made by using a water/solid mixture ratio of 0.30 by mass and then cured for various hydration periods within the range 3 to 90 days. The surface properties of the hydrated samples were studied by means of the nitrogen adsorption technique. The results indicated that the hydrated cement-RHA samples made from rice husks fired at 450 and 700C gave higher values of surface area than that for the hydrated cement-RHA sample made from rice husks fired at 1000C. The surface area and pore volume results could be related to the pore structure of the silica produced in the RHA, as controlled by its predicted degree of crystallinity.     

Reactivity of fly ash in cement paste studied by means of thermogravimetry and isothermal calorimetry

Four paste mixtures with varying replacement level of the cement content by fly ash have been studied. Due to fly ash, the acceleration period decreased and a third hydration peak was noticed with isothermal calorimetry. The total heat after 7 days increased with increasing fly ash content. From 1 to 7 days, thermogravimetry showed a higher chemically bound water and Ca(OH)₂-content for the pastes with fly ash. Between 7 and 14 days the calcium hydroxide started to be depleted due to the pozzolanic reaction. A unique relation was found between calcium hydroxide and total heat development.     

Sulphate resistance and passivation ability of the mortar made from pozzolan cement with zeolite

Sulphate resistance and passivation ability of the mortars made from pozzolan cement of CEM IV/A (P) type according to European Standard EN 197-1 (zeolite blended cement with 60.82 mass% of PC clinker, 35.09 mass% of zeolite and 4.09 mass% of gypsum abbreviated as ZBC) and ordinary Portland cement (abbreviated as PC) are introduced. Resistance tests were performed in water and 5% sodium sulphate solution (both 20°C) for 720 days. The increased sulphate resistance of pozzolan cement relative to that of PC was found. The key quantitative insight into the hydrate phase behaviour is given by thermal analysis. This is due to pozzolanic reaction of zeolite with PC resulting in reduction of the formed Ca(OH)₂ opposite to the reference PC. Ability of pozzolan cements with 15 to 50 mass% of zeolite to protect steel against corrosion was verified in 20°C/85% RH-wet air within 180-day cure. Steel was not corroded in the mortars made with pozzolan cement containing up to 35 mass% of zeolite. Pozzolan cement of CEM IV/A (P) type containing 35 mass% of zeolite is a suitable cementitious material for concrete structures exposed to sulphate attack. Steel is protected against corrosion by this pozzolan cement in the same measure as the reference PC.     

弯曲型Lamb波传播特性与固井质量相关性研究

轻质水泥在油田固井中的广泛应用使得传统测井方式无法有效的对固井水泥胶结质量做出评价。为了研究新的可行的评价方法,本文采用传递矩阵方法对套管中传播的弯曲型Lamb波进行建模,并通过对所建模型进行数值计算研究了套管外水泥等介质的声学参数变化对弯曲型Lamb波衰减率的影响。数值计算的结果表明,弯曲型Lamb波的衰减率与水泥的声学参数以及水泥与套管的胶结状况有较强相关性,据此可对水泥与套管胶结状况进行评价。本文的计算结果与分析对弯曲型Lamb波在水泥胶结评价中的应用具有一定的参考意义。     

铝酸盐水泥矿物结构与性能的量子化学计算研究

用量子化学的电荷自洽离散变分Xα(SCC-DV-Xα)计算方法研究了CaO-Al₂O₃系统五种水泥矿物的结构、性能与化学键之间的关系及固溶的杂质离子Na⁺对矿物性能的影响。计算结果表明:Ca-O共价键强度的次序是C₃A < C₁₂A₇ < CA < CA₂ < CA₆,且各矿物的Ca-O键强度都小于它们的Al-O键强度,与相应的水泥矿物水化活性的实验结果一致。Na⁺固溶于C₃A结构后使其Al-O键增强,水化活化能变大,态密度减小,被认为是Na⁺降低C₃A水化活性的主要原因。