Monitoring the moisture transport in building stones using fibre optic relative humidity sensors

Weathering of stone is one of the major reasons for the damage of stone masonry structures and it takes place due to interlinked chemical, physical and biological processes in stones. The key parameters involved in the deterioration processes are temperature, moisture and salt. It is now known that the sudden variations in temperature and moisture greatly accelerate the weathering process of the building stone fabric. Therefore, in order to monitor these sudden variations an effective and continuous monitoring system is needed. Furthermore, it must consist of robust sensors which are accurate and can survive in the harsh environments experienced in and around masonry structures. Although salt penetration is important for the rate of deterioration of stone masonry structures, the processes involved are much slower than the damage associated with temperature and moisture variations. Therefore, in this paper a novel fibre optic temperature cum relative humidity sensor is described and its applicability in monitoring building stones demonstrated. The performance of the sensor is assessed in an experiment comprising wetting and drying of limestone blocks. The results indicate that the novel fibre optic relative humidity sensor which is tailor made for applications in masonry structures performed well in wetting and drying tests, whilst commercial capacitance based sensors failed to recover during the drying regime for a long period after a wetting regime. That is, the fibre optic sensor has the capability to measure both sorption and de-sorption characteristics of stone blocks. This sensor is used in a test wall in Oxford and the data thus obtained strengthened the laboratory observations.

Using temporal analysis of products and flux response technology to determine diffusion coefficients in catalytic monoliths

The importance of accurately measuring gas diffusivity in porous materials has led to a number of methods being developed. In this study the Temporal Analysis of Products (TAP) reactor and Flux Response Technology (FRT) have been used to examine the diffusivity in the washcoat supported on cordierite monoliths. Herein, the molecular diffusion of propane within four monoliths with differently prepared alumina/CeZrOx washcoats was investigated as a function of temperature. Moment-based analysis of the observed TAP responses led to the calculation of the apparent intermediate gas constant, Kp, that characterises adsorption into the mesoporous network and apparent time delay, tapp, that characterises residence time in the mesoporous network. Additionally, FRT has been successfully adapted as an extensive in situ perturbation technique in measuring intraphase diffusion coefficients in the washcoats of the same four monolith samples. The diffusion coefficients obtained by moment-based analysis of TAP responses are larger than the coefficients determined by zero length column (ZLC) analysis of flux response profiles with measured values of the same monolith samples between 20 and 100 °C ranging from 2–5×10^-9 m² s^-1 to 4–8×10^-10 m² s^-1, respectively. The TAP and FRT data, therefore, provide a range of the lower and upper limits of diffusivity, respectively. The reported activation energies and diffusivities clearly correlate with the difference in the washcoat structure of different monolith samples.

Carbon flow in an upland grassland: effect of liming on the flux of recently photosynthesized carbon to rhizosphere soil

The effect of liming on the flow of recently photosynthesized carbon to rhizosphere soil was studied using (CO2)-C-13 pulse labelling, in an upland grassland ecosystem in Scotland. The use of C-13 enabled detection, in the field, of the effect of a 4-year liming period of selected soil plots on C allocation from plant biomass to soil, in comparison with unlimed plots. Photosynthetic rates and carbon turnover were higher in plants grown in limed soils than in those from unlimed plots. Higher delta(13)C% values were detected in shoots from limed plants than in those from unlimed plants in samples clipped within 15 days of the end of pulse labelling. Analysis of the aboveground plant production corresponding to the 4-year period of liming indicated that the standing biomass was higher in plots that received lime. Lower delta(13)C% values in limed roots compared with unlimed roots were found, whereas no significant difference was detected between soil samples. Extrapolation of our results indicated that more C has been lost through the soil than has been gained via photosynthetic assimilation because of pasture liming in Scotland during the period 1990-1998. However, the uncertainty associated with such extrapolation based on this single study is high and these estimates are provided only to set our findings in the broader context of national soil carbon emissions.

Flux and turnover of fixed carbon in soil microbial biomass of limed and unlimed plots of an upland grassland ecosystem

The influence of liming on rhizosphere microbial biomass C and incorporation of root exudates was studied in the field by in situ pulse labelling of temperate grassland vegetation with (13)CO(2) for a 3-day period. In plots that had been limed (CaCO(3) amended) annually for 3 years, incorporation into shoots and roots was, respectively, greater and lower than in unlimed plots. Analysis of chloroform-labile C demonstrated lower levels of (13)C incorporation into microbial biomass in limed soils compared to unlimed soils. The turnover of the recently assimilated (13)C compounds was faster in microbial biomass from limed than that from unlimed soils, suggesting that liming increases incorporation by microbial communities of root exudates. An exponential decay model of (13)C in total microbial biomass in limed soils indicated that the half-life of the tracer within this carbon pool was 4.7 days. Results are presented and discussed in relation to the absolute values of (13)C fixed and allocated within the plant-soil system.

Moisture and temperature dependence of the dielectric properties of pharmaceutical powders

The dielectric properties of pharmaceutical powder-(paracetamol, aspirin, lactose, maize starch, adipic acid) solvent (water) mixtures were measured at 2,450 MHz at a range of moisture contents (0-1.0 kg kg(-1), dry basis) and temperatures (20-70 A degrees C). The dielectric constant (epsilon'), loss factor (epsilon aEuro(3)) and penetration depth (d (p)) were found to be dependent on frequency, moisture content, temperature and powder type. For powder-water mixtures, a linear increase in the dielectric properties with moisture content was observed, whilst the temperature dependence was of quadratic form. The penetration depth was also significantly affected by temperature and moisture content. Although, epsilon aEuro(3) also increased with increasing temperature, variation with moisture content was temperature dependent. This information on dielectric properties is essential for mathematical description of the pharmaceutical product temperature history during microwave heating and for the design of microwave drying equipment.

Controlled chemistry of Moisture Sensitive Reagents in Ionic Liquids

Many reactions involving phosphorus reagents require highly anhydrous and inert conditions for their successful implementation. In particular, the use of PCl3 and its derivatives for synthesis is often hampered by the inherent sensitivity of the materials themselves. Ionic liquids are emerging as green alternative solvents for a range of processes, and in particular have proven to be excellent media for highly sensitive phosphorus reagents without the need for anhydrous or inert conditions. Herein, we report the use of ionic liquids as both storage and reaction media which allows difficult and sensitive chemistry to be achieved in a more accessible manner.

Soil Moisture Deficit as a predictor of the trend in soil water status of grass fields

Nutrient loss from agricultural land following organic fertilizer spreading can lead to eutrophication and poor water quality. The risk of pollution is partly related to the soil water status during and after spreading. In response to these issues, a decision support system (DSS) for nutrient management has been developed to predict when soil and weather conditions are suitable for slurry spreading. At the core of the DSS, the Hybrid Soil Moisture Deficit (HSMD) model estimates soil water status relative to field capacity (FC) for three soil classes (well, moderately and poorly drained) and has potential to predict the occurrence of a transport vector when the soil is wetter than FC. Three years of field observation of volumetric water content was used to validate HSMD model predictions of water status and to ensure correct use and interpretation of the drainage classes. Point HSMD model predictions were validated with respect to the temporal and spatial variations in volumetric water content and soil strength properties. It was found that the HSMD model predictions were well related to topsoil water content through time, but a new class intermediate between poor and moderate, perhaps ‘imperfectly drained’, was needed. With correct allocations of a field into a drainage class, the HSMD model predictions reflect field scale trends in water status and therefore the model is suitable for use at the core of a DSS.

Self-Similar Nested Flux Closure Structures in a Tetragonal Ferroelectric

In specific solid-state materials, under the right conditions, collections of magnetic dipoles are known to spontaneously form into a variety of rather complex geometrical patterns, exemplified by vortex and skyrmion structures. While theoretically, similar patterns should be expected to form from electrical dipoles, they have not been clearly observed to date: the need for continued experimental exploration is therefore clear. In this Letter we report the discovery of a rather complex domain arrangement that has spontaneously formed along the edges of a thin single crystal ferroelectric sheet, due to surface-related depolarizing fields. Polarization patterns are such that nanoscale “flux-closure” loops are nested within a larger mesoscale flux closure object. Despite the orders of magnitude differences in size, the geometric forms of the dual-scale flux closure entities are rather similar.

Flux of ionic dyes across microneedle-treated skin:effect of molecular characteristics

Drug flux across microneedle (MN)-treated skin is influenced by the characteristics of the MN array, formed microconduits and physicochemical properties of the drug molecules in addition to the overall diffusional resistance of microconduits and viable tissue. Relative implication of these factors has not been fully explored. In the present study, the in vitro permeation of a series of six structurally related ionic xanthene dyes with different molecular weights (MW) and chemical substituents, across polymer MN-pretreated porcine skin was investigated in relation of their molecular characteristics. Dyes equilibrium solubility, partition coefficient in both n-octanol or porcine skin/aqueous system, and dissociation constants were determined. Results indicated that for rhodamine dyes, skin permeation of the zwitterionic form which predominates at physiological pH, was significantly reduced by an increase in MW, the skin thickness and by the presence of the chemically reactive isothiocyanate substituent. These factors were generally shown to override the aqueous solubility, an important determinant of drug diffusion in an aqueous milieu. The data obtained provided more insight into the mechanism of drug permeation across MN-treated skin, which is of importance to both the design of MN-based transdermal drug delivery systems and of relevance to skin permeation research.

Investigation of moisture condition and Autoclam sensitivity on air permeability measurements for both normal concrete and high performance concrete

While on site measurement of air permeability provides a useful approach for assessing the likely long term durability of concrete structures, no existing test method is capable of effectively determining the relative permeability of high performance concrete (HPC). Lack of instrument sensitivity and the influence of concrete moisture are proposed as two key reasons for this phenomenon. With limited systematic research carried out in this area to date, the aim if this study was to investigate the influence of instrument sensitivity and moisture condition on air permeability measurements for both normal concrete and HPC. To achieve a range of moisture conditions, samples were dried initially for between one and 5 weeks and then sealed in polythene sheeting and stored in an oven at 50 C to internally distribute moisture evenly. Moisture distribution was determined throughout using relative humidity probe and electrical resistance measurements. Concrete air permeability was subsequently measured using standardised air permeability (Autoclam) and water penetration (BS EN: 12390-8) tests to assess differences between the HPCs tested in this study. It was found that for both normal and high performance concrete, the influence of moisture on Autoclam air permeability results could be eliminated by pre-drying (50 ± 1 C, RH 35%) specimens for 3 weeks. While drying for 5 weeks alone was found not to result in uniform internal moisture distributions, this state was achieved by exposing specimens to a further 3 weeks of sealed pre-conditioning at 50 ± 1 C. While the Autoclam test was not able to accurately identify relative HPC quality due to low sensitivity at associated performance levels, an effective preconditioning procedure to obtain reliable air permeability of HPC concretes was identified. © 2013 The Authors

Exploring Vertex Interactions in Ferroelectric Flux-Closure Domains

Using piezoresponse force microscopy, we have observed the progressive development of ferroelectric flux-closure domain structures and Landau−Kittel-type domain patterns, in 300 nm thick single-crystal BaTiO3 platelets. As the microstructural development proceeds, the rate of change of the domain configuration is seen to decrease exponentially. Nevertheless, domain wall velocities throughout are commensurate with creep processes in oxide ferroelectrics. Progressive screening of macroscopic destabilizing fields, primarily the surface-related depolarizing field, successfully describes the main features of the observed kinetics. Changes in the separation of domain-wall vertex junctions prompt a consideration that vertex−vertex interactions could be influencing the measured kinetics. However, the expected dynamic signatures associated with direct vertex−vertex interactions are not resolved. If present, our measurements confine the length scale for interaction between vertices to the order of a few hundred nanometers.

Design of a compact spectrometer for high-flux MeV gamma-ray beams

A novel design for a compact gamma-ray spectrometer is presented. The proposed system allows for spectroscopy of high-flux multi-MeV gamma-ray beams with MeV energy resolution in a compact design. In its basic configuration, the spectrometer exploits conversion of gamma-rays into electrons via Compton scattering in a low-Z material. The scattered electron population is then spectrally resolved using a magnetic spectrometer. The detector is shown to be effective for gamma-ray energies between 3 and 20 MeV. The main properties of the spectrometer are confirmed by Monte Carlo simulations.

Localized Flux Maxima of Arsenic, Lead, and Iron around Root Apices in Flooded Lowland Rice

In wetland-adapted plants, such as rice, it is typically root apexes, sites of rapid entry for water/nutrients, where radial oxygen losses (ROLs) are highest. Nutrient/toxic metal uptake therefore largely occurs through oxidized zones and pH microgradients. However, the processes controlling the acquisition of trace elements in rice have been difficult to explore experimentally because of a lack of techniques for simultaneously measuring labile trace elements and O2/pH. Here, we use new diffusive gradients in thin films (DGT)/planar optode sandwich sensors deployed in situ on rice roots to demonstrate a new geochemical niche of greatly enhanced As, Pb, and Fe(II) mobilization into solution immediately adjacent to the root tips characterized by O2 enrichment and low pH. Fe(II) mobilization was congruent to that of the peripheral edge of the aerobic root zone, demonstrating that the Fe(II) mobilization maximum only developed in a narrow O2 range as the oxidation front penetrates the reducing soil. The Fe flux to the DGT resin at the root apexes was 3-fold higher than the anaerobic bulk soil and 27 times greater than the aerobic rooting zone. These results provide new evidence for the importance of coupled diffusion and oxidation of Fe in modulating trace metal solubilization, dispersion, and plant uptake.