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.     

Pillaring and photocatalytic properties of mesoporous α-Fe2O3/titanate nanocomposites via an exfoliation and restacking route

Mesoporous α-Fe₂O₃-pillared titanate nanocomposites have been successfully synthesized through an exfoliation−restacking route. Powder X-ray diffraction and N₂ adsorption-desorption isotherms revealed that the α-Fe₂O₃ pillared titanate has an interlayer distance of 3.27 nm, a specific surface area of 66 m²/g and an average pore size of 7.6 nm, suggesting the formation of a mesoporous pillared structure. UV-vis diffuse reflectance spectra show a red shift, indicative of a narrow band gap energy of ∼2.1 eV compared to the host layered titanate, which is essential in creating a visible light photocatalytic activity. The results of degradation of rhodamine B reveal that the present pillared mesoporous composites exhibit better photocatalytic activities than those of the pristine materials under visible irradiation, based on the band gap excitement and the dye-sensitized path, originated from their high surface area, mesoporosity and the electronic coupling between the host and the guest components.     

Comparative study of silanisation reactions for the biofunctionalisation of Ti-surfaces

In the present work, we report on the biofunctionalisation of silanised Ti-surfaces with gelatin. In recent years, a large number of papers have been published about the silanisation of different substrates including Ti-surfaces for biomedical applications. However, a comparative study evaluating the effects of different pre-treatment methods (cleaning and/or oxidation) and the efficiency of different silanisation reactions has to our information not yet been published. Since a clean and reproducible surface is required for studying structure-property relations, all Ti-surfaces were subjected to a three step procedure including a cleaning step, an oxidation step and a silanisation step. XPS analysis and contact angle measurements revealed that the pre-treatment of the Ti samples (cleaning + oxidation) had a drastic effect both on the surface composition and its wettability. A detailed study on the effect of different silanisation parameters indicated that the siloxane concentration, the siloxane type, the solvent and a catalyst affect the coupling efficiency of siloxanes to Ti-surfaces. Stability studies revealed a dependency between the siloxane type and the stability of the siloxane coating against hydrolytic cleavage from a Ti-surface. Since Ti-surfaces modified with a methacrylate containing silane possessed the highest hydrolytic stability, these surfaces were selected for the subsequent immobilisation of methacrylamide-modified gelatin via high energy irradiation induced cross-linking. The present work clearly demonstrates the need of a proper reaction strategy for immobilising ligands on Ti-surfaces.     

Mechano-thermal nanoparticulate coatings for enhancing the cycle stability of LiCoO2

A mechano-thermal coating method was adopted for obtaining LiCoO₂ coated particles with pre-formed pseudo-boehmite nanoparticulate, followed by calcination at 723 K for 10 h. From X-ray diffraction (XRD) analysis it was seen that the coated cathode materials did not show any extraneous phase peaks corresponding to the pseudo-boehmite and the crystal structure, α-NaFeO₂, remained the same as pristine LiCoO₂. Scanning electron micrograph (SEM) of the coated samples showed that above the 1.0 wt.% coating level, the excess pseudo-boehmite got glued to the coated cathode particles as spherules. TEM images showed that the Al₂O₃ particles derived from pseudo-boehmite formed ∼20 nm thickness coating layer on the LiCoO₂ particles. The XPS/ESCA results revealed that the presence of two different O 1s corresponds to the surface coated Al₂O₃ and the core material. The electrochemical performance of the coated materials by a cycling study suggest that 1.0 wt.% coated Al₂O₃ derived from pseudo-boehmite on the two commercial LiCoO₂ samples improved cycle stability by a factor of five and 11 times over the pristine LiCoO₂ cathode material. Cyclic voltammetry revealed that the hexagonal-monoclinic-hexagonal phase transformations were retained for the coated cathode materials upon continuous cycling.     

Excess surface work—A modelless way of getting surface energies and specific surface areas directly from sorption isotherms

Sorption isotherms can be easily transformed into excess surface work (ESW) isotherms, computed as the product of the adsorbed amount and the change in chemical potential. Plotted against the amount adsorbed at least one minimum is yield. Thermodynamically ESW is the sum of the surface free energy and the isobaric isothermal work of sorption. Therefore, ESW is not a model, instead it is just another way of presenting an isotherm. From the amount adsorbed in the first minimum one can obtain a specific surface area similar to the BET surface area. The depth of the ESW in the minimum gives a sorption energy, which corresponds approximately to the loss of degrees of freedom of the sorptive. In this contribution the ESW plots of various sorption isotherms on highly ordered alumina with cylindrical pores of 25 nm width and mesoporous SBA 15 will be presented and discussed.     

Fundamental processes of aluminium corrosion studied under ultra high vacuum conditions

Surface sensitive electron spectroscopy was applied to study the fundamental processes of aluminium corrosion. We used metastable induced electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS) for the investigation of the densities of states of surface and bulk, respectively. Furthermore we applied X-ray photoelectron spectroscopy (XPS) to investigate the chemical composition of the top surface layers. All measurements were performed under ultra high vacuum conditions.Al films with thicknesses of 7 nm were investigated. Both the interaction of oxygen and water with these films leads to the formation of an aluminium-oxygen layer, which is partly composed of stoichiometric Al₂O₃. Weak heat treatment at 770 K transforms the surface layer into Al₂O₃ with a thickness of about 2 nm. Further gas offer does not lead to an increase of this thickness, neither for oxygen nor for water. Additional to the oxygen offer, water exposure leads to the formation of OH species in the top aluminium-oxygen layer to a small amount. Weak heat treatment to 770 K removes this species completely. Water exposure leads to a much faster oxide formation than oxygen exposure. We try to give a model for the fundamental corrosion processes on a molecular scale.     

Characterization of water exposed plasma sprayed oxide coating materials using XPS

The surface compositions and oxidation states of non-exposed and water exposed plasma sprayed oxide coatings were studied using X-ray photoelectron spectroscopy (XPS). Coating materials were TiO₂, Al₂O₃ and Cr₂O₃ and their mixtures. Water exposures were performed for free standing coating disks at mild electrolyte (1 mmol NaCl solution) at pH 4, 7 and 9. The exposure time was two weeks.It was observed that pure plasma sprayed TiO₂ material was chemically stable over whole experiment pH range and only slight surface hydroxylation was observed for this material.In case of plasma sprayed Al₂O₃ materials the surface O/Al ratio increased considerably during water exposure especially at exposure pH 7. This was probably result of surface conversion to hydrous form. No surface oxidation state changes were observed for this material.The non-exposed Cr₂O₃ materials contained both Cr(III) and Cr(VI) oxides. The water exposures increased the surface oxygen and Cr(VI) contents at the expense of Cr(III). The most probable reason for that was the dissolution of surface Cr(VI) oxide phase during water exposures and the (re)adsorption of dissolved Cr(VI) species back to the surface.     

First nucleation steps of vanadium oxide thin films studied by XPS inelastic peak shape analysis

The initial states of deposition of vanadium oxide thin films have been studied by analysis of the peak shape (both inelastic background and elastic contributions) of X-ray photoemission spectra (XPS) after successive deposition experiments. This study has permitted to assess the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of a XPS spectrometer. Thin films of vanadium oxide have been prepared on Al₂O₃ and TiO₂ by means of thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition. The thin films prepared by the first two procedures consisted of V₂O₄, while those prepared by the latter had a V₂O₅ stoichiometry. The analysis of the inelastic background of the photoemission spectra has shown that the films prepared by thermal evaporation on Al₂O₃ are formed by big particles that only cover completely the surface of the substrate when their height reaches 16 nm. By contrast, the thin films prepared with assistance of ions on Al₂O₃ or with plasma on TiO₂ consist of smaller particles that succeed in covering the substrate surface already for a height of approximately 4 nm. Thin films prepared by plasma-assisted deposition on Al₂O₃ depict an intermediate situation where the substrate is completely covered when the particles have a height of approximately 6 nm. The type of substrates, differences in the deposition procedure or the activation of the adatoms by ion bombardment are some of the factors that are accounted for by to explain the different observed behaviours.     

Magnetic hydrophobic nanocomposites: Silica aerogel/maghemite

Magnetic hydrophobic aerogels (MHA) in the form of nanocomposites of silica and maghemite (γ-Fe₂O₃) were prepared by one step sol–gel procedure followed by supercritical solvent extraction. Silica alcogels were obtained from TEOS, MTMS, methanol and H₂O, and Fe(III) nitrate as magnetic precursor. The hydrophobic property was achieved using the methytrimethoxysilane (MTMS) as co-precursor for surface modification. The so produced nanocomposite aerogels are monolithic, hydrophobic and magnetic. The interconnected porous structure hosts ∼6 nm size γ-Fe₂O₃ particles, has a mean pore diameter of 5 nm, and a specific surface area (SSA) of 698 m²/g. Medium range structure of MHA is determined by SAXS, which displays the typical fractal power law behavior with primary particle radius of ∼1 nm. Magnetic properties of the nanoparticle ensembles hosted in them are studied by means of dc-magnetometry.     

Electromagnetic wave absorption properties of Fe3C/carbon nanocomposites prepared by a CVD method

Dendrite-shaped iron nanowires with 50-200 nm in diameter and 10-20 μm in length were prepared by the CVD method from Fe(CO)₅ as a starting source. Ethanol was cracked on the surface of the resultant iron nanowires to form the Fe₃C/carbon nanocomposites, in which nanosized carbon beads covered the surface of Fe₃C. Resin compact of the resultant Fe₃C/carbon nanocomposites had excellent electromagnetic wave absorption ability in the range of 0.9-9.0 GHz, and such available absorption range more enhanced compared to that observed on the resin compact prepared from the original iron nanowires by the hybridization of magnetic (Fe₃C) and dielectric (carbon) materials.     

Diffusivity control in nanoporous membrane through organic-inorganic hybridization

Nanoporous inorganic materials have attracted great interest due to their potential application as nanofilters, drug delivery carriers and adsorbents. In order to control the molecular passage through nanopores, we have modified the pore channel of inorganic materials with organic moieties and investigated the diffusion pattern of small molecules. The surface was modified by octyltriethoxysilane (OTS) by refluxing in toluene for 12 h. The water contact angle of OTS modified zirconia membrane was observed ∼110° showing hydrophobic surface. Contact angles to various solvents were also examined to verify the self-assembled monolayer of octyl chains on the inorganic membrane. The molecular passage patterns of both pristine and modified nanoporous membrane were evaluated by means of the diffusivity of small dye molecule, azobenzene. The diffusion coefficients of azobenzene on both membranes were measured in various solvents on the basis of Fick’s diffusion law. The diffusivities in various solvents for pristine and its modified zirconia membrane were determined. The diffusivity was observed to be influenced by surface energy of both membrane and solvent as well as the polarity of solvents.     

Visible luminescence of Al2O3 nanoparticles embedded in silica glass host matrix

This paper deals with the sol-gel elaboration and defects photoluminescence (PL) examination of Al₂O₃ nanocrystallites (size ∼30 nm) confined in glass based on silica aerogel. Aluminium oxide aerogels were synthesized using esterification reaction for hydrolysis of the precursor and supercritical conditions of ethyl alcohol for drying. The obtained nanopowder was incorporated in SiO₂ host matrix. After heating under natural atmosphere at 1150 °C for 2 h, the composite Al₂O₃/SiO₂ (AS) exhibited a strong PL bands at 400-600 and 700-900 nm in 78-300 K temperature range. PL excitation (PLE) measurements show different origins of the emission. It was suggested that OH-related radiative centres and non-bridging oxygen hole centres (NBOHCs) were responsible for the bands at 400-600 and 700-900 nm, respectively.     

Simulation of KrF laser ablation of Al2O3-TiC

Previous work by the authors on micromachining of Al₂O₃-TiC ceramics using excimer laser radiation revealed that a columnar surface topography forms under certain experimental conditions. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations show that the columns develop from small globules of TiC, which appear at the surface of the material during the first laser pulses. To understand the mechanism of formation of these globules, a 2D finite element ablation model was developed and used to simulate the time evolution of the temperature field and of the surface topography when a sample of Al₂O₃-TiC composite is treated with KrF laser radiation. Application of the model showed that the surface temperature of TiC rises much faster than that of Al₂O₃, but since TiC has a very high boiling temperature, its vaporization is significant only for a short time. By contrast, the surface temperature of Al₂O₃ rises above its boiling temperature for a much longer period, leading to a greater ablation depth than TiC. As a result, a small TiC globule stands above the Al₂O₃ surface. The results of the model are compared with experimental measurements performed by AFM. After three pulses, the height of the globules predicted by the model is about 340 nm, in good agreement with the height measured experimentally, about 400 nm.     

Water vapour sorption by mim systems

In studying the properties of the sandwich system Al-Al₂O₃-Au(Al) the capacitance of the system was found to depend on the humidity of the environment. The humidity induced capacitance change is reversible and can be explained assuming a process of physical sorption of water vapours by Al₂O₃ dielectric film. The sorption rate is independent of the oxide film thickness, which leads to a conclusion that mainly the sorption in the surface layer of the oxide is involved in the process. The sorption rate is, however, decreasing with increasing thickness of the upper evaporated electrode, which can be taken as an evidence of the fact that the water molecules penetrate to the oxide films through the upper metal layer whose coverage is not complete due to the porosity of the oxide film underneath.On the basis of our experimental results we come to a conclusion that even when the Al₂O₃ films are prepared by oxidation in a 3% solution of tartaric acid, their structure is porous. Proceeding from a simplified picture of the dielectric structure we propose an equivalent electrical scheme of the Al-Al₂O₃-Au Al system. The frequency characteristics measured at different environment humidities correspond to the dependences calculated for the proposed equivalent circuit.     

Electron microscopic study on interfacial characterization of electroless Ni-W-P plating on aluminium alloy

The interface between electroless plating Ni-W-P deposit and aluminium alloy (Al) matrix at different temperature heated for 1 h was studied using transmission electron microscope. The results show that the interface between as-deposited Ni-W-P deposit and Al matrix is clear. There are no crack and cavity. The bonding of Ni-W-P deposit and Al matrix is in good condition. The Ni-W-P plating is nanocrystalline phase (5-6 nm) in diameter. After being heated at 200 °C for 1 h, the interface of Ni-W-P deposit and Al matrix is clear, without the appearance of the diffusion layer. There exist a diffusion layer and educts of intermetallic compounds of nickle and aluminium such as Al₃Ni, Al₃Ni₂, NiAl, Ni₅Al₃ and so on between Ni-W-P deposit and Al matrix after being heated at 400 °C for 1 h.     

A numeric model for the kinetics of water vapor sorption on cellulosic reinforcement fibers

Some natural fibers like flax, hemp and others show excellent mechanical properties that make them a promising choice for the reinforcement of polymers. The increasing research on natural fiber reinforced composites has still left important questions open, mainly concerning the fiber–matrix interface. Compared to the well optimized glass fibers, cellulose fibers show very different interaction with matrix polymers and adhesion promoters. The hydrophilic cellulose structure allows for the penetration of a considerable amount of water into the amorphous regions of the fibers, eventually exceeding 20% by mass, depending on fiber type, preparation and environmental humidity. Even embedded in totally apolar polymers the cellulose partly retains its ability for water sorption, which results in unfavorable effects, such as dimensional changes, decrease in strength, roughening of the surface, etc. The interaction of differently prepared fibers with water vapor and the effect of surface treatment is investigated by measuring the dynamics of water vapor sorption. An exponential model is used for the numerical evaluation of the sorption and desorption kinetics. The model not only allows for an excellent fit of the experimental isotherms, but without any further assumptions it immediately gives evidence of the existence of two distinct mechanisms for the exchange of water vapor, related to different sorption sites. These specific mechanisms are represented by individual sorption–desorption isotherms as components of the total isotherms. The model provides a clearer differentiation of the effects of fiber preparation and modification with respect to interfacial interactions.     

爆轰裂解法制备纳米石墨粉的吸附性能研究

 在酸含量不同的原材料中,通过爆轰的方法制备纳米石墨粉,并利用BET方程以及BJH方法对所得纳米石墨粉进行比表面积和孔径分布分析。分析结果表明,所得爆轰产物中有的比表面积大致为天然鳞片石墨的5.3~9.2倍,而且随酸含量的增大逐渐增大,产物的等温线中存在吸附滞后现象。其中,增大的比表面积主要由分布在3 nm至7 nm之间的孔引起的,而且在爆轰后,孔径4 nm左右的孔,其数量达到最大值。通过对纳米石墨粉的研究,分析了酸在爆轰过程中的积极作用,并为纳米石墨粉的进一步应用提供了结构信息。     

Structures of Co and Pt nanoclusters on a thin film of Al2O3/NiAl(1 0 0) from reflection high-energy electron diffraction and scanning-tunnelling microscopy

With reflection high-energy electron diffraction (RHEED) and scanning-tunnelling microscopy (STM), we made measurements on Co and Pt nanoclusters grown by vapour deposition on a thin film of Al₂O₃/NiAl(1 0 0). The results show that the annealed Co nanoclusters (with mean diameters 2.5, 3.4, 5.8 nm and heights 0.7, 1.5, 1.5 nm, respectively) and Pt nanoclusters (with mean diameter 2.25 nm and height 0.4 nm) are highly crystalline and that their structures are significantly affected by the oxide substrate. Structural analysis based on the RHEED patterns indicates that both Co and Pt clusters have a fcc phase and grow with their (0 0 1) facets parallel to the θ-Al₂O₃(1 0 0) surfaces, and with their [1 1 0] and [−1 1 0] axes along the [0 1 0] and [0 0 1] directions of the oxide surface, respectively, so (Co(0 0 1)[1 1 0]∥Al₂O₃(1 0 0)[0 1 0] and Pt(0 0 1)[1 1 0]∥Al₂O₃(1 0 0)[0 1 0]). This growth is optimal as the Co and Pt fcc (0 0 1) facets match well with the oxygen mesh. To minimize the lattice mismatch, the lattice parameter of the Co clusters expands 4-5% relative to fcc Co bulk, whereas the lattice parameter of the Pt clusters remains near the bulk value, as the Pt fcc (0 0 1) plane has a close lattice match with the oxide surface.     

Engineering of hydrophilic and plasmonic properties of Ag thin film by atom beam irradiation

Hydrophilic Ag nanostructures were synthesized by physical vapour deposition of 5 nm Ag thin films followed by irradiation with 1.5 keV Ar atoms. Optical absorbance measurements show a characteristic surface plasmon resonance absorption band in visible region. A blue-shift in absorbance from 532 to 450 nm is observed with increasing fluence from 1 × 10¹⁶ to 3 × 10¹⁶ atoms/cm². Atomic force microscopy was performed for the pristine and irradiated samples to study the surface morphology. The atom beam irradiation induced sputtering and surface diffusion lead to the formation of plasmonic surface. Rutherford backscattering spectroscopy of the pristine and irradiated film indicates that metal content in the film decreases with ion fluence, which is attributed to the sputtering of Ag by Ar atoms. The contact angle measurement demonstrates the possibility of engineering the hydrophilicity by atom beam irradiation.     

Ablation characteristics of aluminum oxide and nitride ceramics during femtosecond laser micromachining

Femtosecond laser ablation of aluminum oxide (Al₂O₃) and aluminum nitride (AlN) ceramics was performed under normal atmospheric conditions (λ = 785 nm, τ_p = 185 fs, repetition rate = 1 kHz), and threshold laser fluencies for single- and multi-pulse ablation were determined. The ablation characteristics of the two ceramics showed similar trends except for surface morphologies, which revealed virtually no melting in Al₂O₃ but clear evidence of melting for AlN. Based on subsequent X-ray photoelectron spectroscopy (XPS) analyses, the chemistry of these ceramics appeared to remain the same before and after femtosecond laser ablation.