Deterioration of iron archaeological artefacts: micro‐Raman investigation on Cl‐containing corrosion products

Deterioration after excavation of archaeological iron artefacts buried in soil is often associated with the presence of chlorinated phases in corrosion products, leading to serious problems for conservation of metallic objects of cultural heritage. Therefore, in order to better understand the corrosion process related to the presence of chlorine, some high‐resolution techniques of material characterisation are implemented. The analyses are realised on cross sections of corroded iron objects excavated from archaeological sites dated from the 12th to the 16th century A.D. Cl‐containing phases appear even when the Cl level in the water is low. In addition to the common oxy‐hydroxide‐containing chloride, akaganeite (β–FeOOH) often mentioned in the literature, a ferrous hydroxychloride β–Fe₂(OH)₃Cl was also found in the corrosion layers. Moreover, part of the study is based on the preparation and desalinisation of pure akaganeite powder in order to characterise the influence of the chloride content on its crystalline structure as characterised by Raman spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

Theoretical and experimental study of structures and properties of cement paste: The nanostructural aspects of C-S-H

Ordinary Portland cement (OPC) paste with water to cement ratio 0.5 has been studied by FTIR spectroscopy and TEM/SAED techniques. The progressive shift in frequencies and change in intensity of characteristic peaks in the FTIR spectra of cement powder indicate polymerization of silicates due to hydration reaction. The appearance of new peaks around 975-985 and 3640-3650 cm⁻¹ in FTIR spectra of cement paste has been attributed to the formation of two principal hydration products (C-S-H) and Ca(OH)₂, respectively. There is a strong resemblance of peak shape at 980 cm⁻¹ of cement paste with that of synthesized 1.1 nm Tobermorite. TEM/SAED techniques reveal the presence of three distinct types of C-S-H nanostructures viz. spherical particles, fibres and bundle of fibres, and nano tubes in cement paste. Theoretical study of two C-S-H clusters by MNDO and Density Functional Techniques shows excellent agreement between computed structural data and reported experimental results of Tobermorite and Jennite. The computed interplanar Ca-Ca distance (11.162 Å) of C-S-H cluster (Ca/Si=1.125) indicates greater structural similarity of this cluster to 11 Å Tobermorite. There is a strong similarity of IR profile of C-S-H cluster (Ca/Si=1.125) with 1.1 nm Tobermorite. Above study indicates that this cluster is probably the most likely basic unit of C-S-H phases formed during the early stage of OPC cement hydration.     

The influence of hydration time on the Ni uptake by cement

In this study, Ni uptake by hardened cement paste has been investigated with the aim of improving our understanding of the immobilization process of Ni(II) in cement and the influence of the hydration time on the Ni speciation on the microscopic scale. Information on the Ni distribution and speciation of the Ni phases formed in the cement system has been gained by employing synchrotron-based μ-X-ray fluorescence (μ-XRF) and μ-X-ray absorption spectroscopy (μ-XAS). The Ni-doped cement samples were prepared at a water/cement ratio of 0.4 and with a metal loading of 5000 mg/kg using a sulphate-resisting Portland cement. The samples were hydrated for six hours and one year to account for the chemical environment in a fresh and aged cement paste, respectively. The μ-XAS measurements reveal that a mixture of Ni phases is formed at single regions of interests, independent of the hydration time. Data analysis further indicates that Ni(II) is predominantly immobilized in a layered double hydroxide (LDH, Ni-Al LDH) and only to a minor extent precipitates as Ni-hydroxides. A comparison of the results from this micro-spectroscopic investigation with those from an earlier macro-spectroscopic study, indicate that the same Ni phases are formed both on the macro- and micro-scale.     

Spectral Characteristics of Salinized Soils during Microbial Remediation ProcessesSCIEI北大核心CSCD

In this study, the spectral reflectance of saline soils, the associated soil salt content(SSC) and the concentrations of salt ions were measured and analysed by tracing the container microbial remediation experiments for saline soil (main salt is sodium chloride) of Dongying City, Shandong Province. The sensitive spectral reflectance bands of saline soils to SSC, Cl- and Na+ in the process of microbial remediation were analysed. The average dimension reduction of these bands was conducted by using a combination of correlation coefficient and decision coefficient, and by gradually narrowing the sampling interval method. Results showed that the tendency and magnitude of the average spectral reflectance in all bands of saline soils during the total remediation processes were nearly consistent with SSC and with Cl- coocentration, respectively. The degree of salinity of the soil, including SSC and salt ion concentrations, had a significant positive correlation with the spectral reflectance of all bands, particularly in the near-infrared band. The optimal spectral bands of SSC were 1 370 to 1 445 nm and 1 447 to 1 608 nm, whereas the optimal spectral bands of Cl- and Na+ were 1 336 to 1 461 nm and 1 471 to 1 561 nm, respectively. The relationship model among SSC, soil salt ion concentrations (Cl- and Na+) and soil spectral reflectance of the corresponding optimal spectral band was established. The largest R-2 of relationship model between SSC and the average reflectance of associated optimal band reached to 0.95, and RMSEC and RMSEP were 1.076 and 0.591, respectively. Significant statistical analysis of salt factors and soil reflectance for different microbial remediation processes indicated that the spectral response characteristics and sensitivity of SSC to soil reflectance, which implied the feasibility of high spectrum test on soil microbial remediation monitoring, also provided the basis for quick nondestructive monitoring soil bioremediation process by soil spectral reflectance.     

Electrochemical Studies of Polymeric Carbons. II. Surface Layer Formation on Glassy Carbon Electrodes in Chloride Solutions as Studied by Radiotracer Techniques

The interaction of chloride ions with glassy carbon electrodes is studied by means of ³⁶Cl as radiotracer. Chloride ions are bonded on the electrode in case of anodization depending on electrode potential and duration of the polarization. Strong interaction is observed at electrode potentials more positive than +1.3 V. A significant part of the chloride ions bonded at the glassy carbon can not be displaced neither by cathodic polarization nor by rinsing with water or non-labelled solutions. It is concluded that chloride ions are chemically bonded at the surface and the surface region of glassy carbon.     

应用分子动力学模拟和拉曼光谱对钙、镁、氯离子 水化现象的研究

应用分子动力学方法,模拟了298 K下,密度为1.0 g/cm~3的水溶液中Ca²⁺,Mg²⁺,Cl~-的水化现象,得到了相应离子周围水分子的微观分布情况.发现在钙离子周围,水分子以其氧离子去靠近中心离子;而在氯离子周围,水分子则以其中的一个氢原子去靠近中心离子.通过分析三种离子的径向分布函数、配位数曲线、水化数、水化半径,发现Ca²⁺的水化数和水化半径均大于Mg²⁺,即Ca²⁺的水合能力比Mg²⁺强.与以往研究结果相比,本文计算所得的自扩散系数更接近实验所得结果.为了使模型更好的代表真实水溶液体系,本文还应用分子动力学和拉曼光谱法研究了不同浓度的CaCl₂水溶液.分子动力学研究发现随着浓度的升高,CaCl₂溶液中Ca²⁺,Cl~-的配位数分别呈降低趋势.同时,随着浓度的升高,Ca²⁺,Cl~-的自扩散系数也呈现降低的趋势.作者推断这是由于浓度的升高,加剧了离子的微观反...     

The effect of silica nanoparticles on the pore structure of hydrating cement paste: a spatially resolved low-field NMR study

ABSTRACT

The hydration process of four different cement-based materials at different depths inside the sample was investigated using localised nuclear magnetic resonance relaxation measurements. All the samples are based on white Portland cement (CEM I 42.5 R), with a water-to-cement ratio of 0.5. One sample is a simple cement paste and the other three additionally contain 5% (by mass of cement) silica nanoparticles (50–200?nm size), silanised silica nanoparticles (with silane A 174) or silica fume (80% silica; 0.15?µm average size). The localised transverse relaxation measurements were performed using a single-sided NMR instrument. The relaxation rates were monitored for 48?h during the hydration process at different depths inside the sample. The results showed that the presence of nanoparticles influences not only the speed of hydration overall, but also the homogeneity of the materials.     

Catalytic behavior of graphene oxide for cement hydration process

Hydration is a critical step that determines the performance of cement-based materials. In this paper, the effect of GO on the hydration of cement was evaluated by XRD and FTIR. It was found that GO can remarkably accelerate the hydration rate of cement due to its catalytic behavior. This happened because the oxygen-containing functional groups of GO provide adsorption sites for both water molecules and cement components.     

修复过程中盐渍化土壤的光谱特征分析

该研究跟踪山东东营盐渍化土壤(盐分主要以氯化钠为主)的微生物修复盆栽实验,分析研究修复过程中土壤理化性质的改良以及相应的光谱特征变化。基于对修复过程中不同阶段土壤盐分含量(SSC)和Na+,Cl-等理化指标的化学分析及其同步的光谱测试,采用平均值降维方法,相关系数与决定系数相结合的方式,通过逐步缩小采样间隔,分析了土壤在微生物修复过程中盐分和盐分离子含量变化及其光谱响应的最佳波段和特征。结果表明,土壤在不同处理的微生物修复过程中,全波段平均光谱反射率与SSC的变化趋势和幅度几近一致,与Cl-含量变化趋势和幅度完全一致。在光谱测试的全波段范围内,SSC及盐分离子含量与光谱反射率呈显著正相关,在近红外波段的反射率变化尤为显著。在此基础上,基于调整光谱采样间隔方法分析获得的盐分及其离子含量最佳光谱响应波段反射率,建立了土壤光谱反射率与盐分含量及其离子含量的关系模型。其中SSC的最佳响应波段1 370～1 445和1 447~1 608 nm,Cl-,Na+的最佳响应波段分别为1 336~1 461和1 471~1 561 nm,建立的模型其R2最高值达到了0.95,RMSEC,RMSEP最大值分别为1.076和0.591。不同处理的土壤微生物修复结果的显著性统计分析及其相应的光谱特征变化,充分显示了土壤盐分含量的光谱响应特征及其敏感性,对发展基于高光谱的土壤盐渍化快速分析诊断方法具有重要意义。     

Mössbauer investigation of the influence of the sea atmosphere on the corrosion of steel constructions in Sochi

A study of the sea atmosphere influence on the corrosion products of steel constructions near Sochi at difference distances from the sea has been made. The phases and compositions of the corrosion products formed on different sides of steel construction elements were examined by using Mössbauer spectroscopy (at 298 and 78 K). The results show that phases and composition distributions in oxide films are different on different parts of the constructions. The differences depend not only on the distance from the sea, but from their relative orientation to the sea also. The phase structure of the oxide films on different positions is identified.     

Effect of the fluid in the inclusions of cement paste on the ultrasonic velocity

The durability of cement composites significantly depends on the movement of the fluids into the material through the porous system. The aqueous phase contained in the pores can cause irreversible damage from the dimensional stability viewpoint. In this sense, methods for non-destructive characterization of both, the porous structure and water content should be investigated. In this work, the effect of the fluid in the inclusions of the cement paste on the ultrasonic velocity is studied. Firstly, a theoretical analysis based on the micromechanical model, considering the microstructural information of the matrix and the fluid filling the pores, is presented. Some experimental work is made later using cement paste samples, whose porous structure is maintained dry or saturate with water. In both cases, the ultrasonic velocity is measured and compared to the one predicted by the micromechanical model. Using this technique, the ultrasonic velocity can be predicted with errors below 2% in the cases of dry or water saturated cement paste.     

水泥老化过程中水动态的准弹性中子散射(QENS)谱分析

准弹性中子散射(quasi-elastic neutron scattering, QENS)实验是研究水泥老化过程中水动态的一种新颖的实验方法.本文利用老化时间分别为7, 14和30 d水泥样品的QENS谱实验数据, 通过应用四个高斯项的和的能量分辨函数R(Q, E)代替一个高斯项的能量分辨函数来改进经验扩散模型(empirical diffusion model, EDM), 再进行非线性最小二乘拟合.由此导出水泥样品中水动态的相关物理参数: 不动水数密度A, 自由水指数FWI=B₁/(A+B₁+B₂), 洛伦兹函数的半高宽Γ, 移动水跳跃之间的平均停留时间τ ₀及自扩散系数D_t, 而且可得出更为精准的QENS谱拟合曲线.拟合得到的物理参数可定量描述水泥老化过程中水动态过程, 从而为QENS实验在水泥老化过程中水动态研究的应用提供一种合理实用的谱分析方法.     

Dynamic crossover in hydration water of curing cement paste: the effect of superplasticizer

The influence of a new comb-shaped polycarboxylate-based superplasticizer (CSSP) on the hydration kinetics and transport properties of aged cement pastes has been investigated by high-resolution quasi-elastic neutron scattering (QENS) and low temperature differential scanning calorimetry (LT-DSC). A new method of analysis of QENS spectra is proposed. By applying the refined method we were able to access to four independent physical parameters including the self-diffusion coefficient of the hydration water confined in the cement paste. Mean squared displacement (MSD) of the hydrogen atom for mobile water molecules displays a dynamic crossover temperature in agreement with DSC data. The experimental results indicate that CSSP polymer added into cement paste moderates the hydration process and decreases the dynamic crossover temperature of the hydration water.     

Investigation of Cl corrosion products of iron archaeological artefacts using micro-focused synchrotron X-ray absorption spectroscopy

Synchrotron-based micro-X-ray absorption spectroscopy is used in the present study to obtain chemical information at the microscopic scale such as coordination and oxidation state of Fe atoms in phases constituting corrosion products within archaeological iron artefacts buried in soil. This technique is required in order to answer questions about the iron corrosion process related to the presence of chloride, particularly for restoration and conservation of metallic artefacts of the cultural heritage. The samples available for X-ray microprobe analyses are cross sections from corroded iron archaeological objects. Previously, complementary techniques have been used such as μXRD and μRaman. This specific study applies micro-X-ray absorption spectroscopy to determine the spatial variation of the predominant Fe oxidation state and to identify the corresponding crystallographic phase. The analyses performed at Fe and Cl K-edges (μXANES) reveal the correlation between the valence distribution in the corrosion products and the evolution of the chloride concentration. In addition to the presence of the well-known iron oxyhydroxide β-FeOOH: akaganeite, we highlight the presence of another important phase, the β-Fe₂(OH)₃Clhydroxychloride. These important findings help to gain new insights concerning the influence of such phases in the iron corrosion mechanism within their precise characterization. PACS 61.10.Ht; 61.10.-i; 68.49.Uv     

一青铜耳杯锈蚀的拉曼光谱分析

利用超景深显微镜和激光共聚焦显微拉曼光谱仪,对重庆市云阳县丝栗包遗址出土的一件青铜耳杯的锈蚀产物进行分析。通过分析可知,该耳杯的锈蚀物主要有:磷氯铅矿(Pb_5(PO_4)_3Cl)、白铅矿(PbCO_3)、氧化铅(PbO)、赤铜矿(Cu_2O)、孔雀石(Cu_2CO_3(OH)_2)和蓝铜矿(Cu_3(CO_3)_2(OH)_2)。铅的腐蚀产物由内向外的分布为氧化铅、白铅矿和磷氯铅矿。据此推断锈蚀外层磷氯铅矿的形成过程可能为:铅氧化成氧化铅,之后转换成白铅矿,白铅矿在酸性、富含磷和氯的环境下转变成化学性质稳定的磷氯铅矿。     

NMR T1–T2 correlation analysis of molecular absorption inside a hardened cement paste containing silanised silica fume

ABSTRACT

The influence of silanised silica fume addition on the pore size distribution and wettability of white cement paste was investigated using T₁–T₂ correlation nuclear magnetic resonance (NMR) relaxometry. Surface silanisation of silica fume particles was achieved by the hydrolysis reaction of APTES (3-Aminopropyltriethoxysilane) and condensation of the silanol functional groups on the surface. The methods used for characterisation of the silanised silica fume particles were scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). By adding silanised silica fume to the cement paste, the accessibility of water molecules to the porous system becomes restricted, leading to a lower permeability in comparison with the unmodified cement paste. Differential scanning calorimetry (DSC) measurements on the cement pastes saturated with Octamethylcyclotetrasiloxane confirm also that the size of inter-C–S–H and capillary pores is not influenced by the addition of silica fume in a detectable manner.     

Salt effects on water/hydrophobic liquid interfaces: a molecular dynamics study

We investigate structural and dynamical properties of NaCl and KCl solution/n-decane interfaces. We find that K(+) and Cl(-) ions localize close to the interface and modify the orientations of both first-layer and second-layer water molecules in the interfacial region. Na(+) and Cl(-) ions are also localized; however, they do not affect the orientation significantly. NaCl salts cause an increase of the surface tension and the residence time of interfacial water molecules. They also decrease the residence time of interfacial n-decane molecules. KCl salt has similar effects, although to a smaller extent. These findings may help us to better understand biological interfaces in physiological solutions.     

Laser-Induced Current Switching Observed in the Discharge Media of CF2Cl2-N2 and CH3Cl-N2

Switchings of discharge current induced by ArF and KrF laser pulses in the discharge media of CF2Cl2-N2 and CH3Cl-N2 were investigated using a negative point-to-plane discharge apparatus. The electron attachment rate constants of CF2Cl2 in buffer gases of N2 and Ar were measured by a parallel-plate drift-tube apparatus at various E/N, from which the dominant negative ions in the discharge media were inferred. The conductivity of the discharge medium is enhanced upon laser irradiation due to conduction electrons being produced from photoelectron-detachment of Cl-. From the dependence of the enhanced current on laser power, the photodetachment cross sections of Cl- in a given discharge condition were derived to be 2.5 × 10-17 cm2 at 193 nm and 1.0 × 10-17 cm2 at 248 nm. After the current enhancement, the current was greatly reduced as was observed in the discharge medium of CF2Cl2-N2, but not in CH3Cl-N2. The mechanism for the optically induced reduction of discharge current is discussed.     

Cracks and pores – Their roles in the transmission of water confined in cementitious materials

Cement paste is formed through a process called hydration by combining water with a cementitious material. Concrete, the worlds most versatile and most widely used material, can then be obtained when aggregates (sand, gravel, crushed stone) are added to the paste. The quality of hardened concrete is greatly influenced by the water confined in the cementitious materials and how it is transmitted through cracks and pores. Here we demonstrate that the water transport in cracks and capillary pores of hardened cement pastes can be approximately modeled by simple equations. Our findings highlight the significance of arresting the development of cracks in cementitious materials used in repository barriers. We also show that neutron scattering is an advantageous technique for understanding how water transmission is effected by gel pore structures. Defining measurable differences in gel pores may hold a key to prediction of the reduction of water transport through cement barriers.     

Salt permeation and exclusion in hydroxylated and functionalized silica pores

We use combined ab initio molecular dynamics (AIMD), grand canonical Monte Carlo, and molecular dynamics techniques to study the effect of pore surface chemistry and confinement on the permeation of salt into silica nanopore arrays filled with water. AIMD shows that 11.6 A diameter hydroxylated silica pores are relatively stable in water, whereas amine groups on functionalized pore surfaces abstract silanol protons, turning into NH3+. Free energy calculations using an ab initio parametrized force field show that the hydroxylated pores strongly attract Na+ and repel Cl- ions. Pores lined with NH3+ have the reverse surface charge polarity. Finally, studies of ions in carbon nanotubes suggest that hydration of Cl- is more strongly frustrated by pure confinement effects than Na+.