Professor Peter McDonald

The changes in microstructure and content of water phases during hydration of a 3:1 BFS:OPC blend are investigated by Mercury Intrusion Porosimetry (MIP), freeze-drying, Thermal Gravimetric Analysis (TGA) and 1H Nuclear Magnetic Resonance (NMR) relaxometry. MIP indicates that during the blend hydration, a reduction in the population of capillary pores (larger than about 100 nm) occurs while the population of gel pores (smaller than few tens of nanometres) increases. Between 3 and 90 days, the porosity estimated by MIP decreases from about 36% down to 18% while the median pore size decreases from about 140 nm down to 6 nm. 1HNMR relaxometry shows that after 1 day of hydration, nearly 70% of the evaporable water is held in capillary pores while about 30% is present in gel pores. After two weeks, most of the evaporable water (90%) is found in pores smaller than few tens of nanometres. : The amount of evaporable water detected by freeze drying decreases from less than 20 wt.% after one week of hydration down to about 16.3 wt.% after 90 days while the amount of chemical ly bound water related to the degree of advancement of the cement hydration and detected by TGA increases from 8 wt.% to 10.3 wt.%. During hydration the BFS:OPC blend matrix evolves from an open microporous network to one of a poorly connected network of water rich nanopores with increasing amounts of chemically bound water. © 2006 Materials Research Society.

The role of a PhD programme is to train students for a career in research – be it at university or in industry. In our experience, almost all physics students who begin a PhD hope for an academic career, yet the overwhelming majority eventually move into industry where they contribute hugely to the research and development of firms. Although this picture seems to be accepted by those now embarking on a PhD, many students still have little idea how they could exploit their physics PhD beyond the narrow confines of their research project. In 2008 – a difficult time for UK physics, which suffered funding cuts and department closures – nine university departments in the south east of England came together to form the South East Physics network (SEPnet). This collaboration helped revive physics in the region by focusing on outreach as well as student employability via a summer industry placement scheme. In 2013 SEPnet launched GRADnet to give PhD physics students greater awareness of opportunities outside academia and a broader set of the skills that are needed to exploit them.

This paper presents summary results of a Round Robin Trial to examine the reproducibility and robustness of 1H NMR relaxation analysis of water in cements. The results have elsewhere been used to evidence a good practice guide for the characterization of cement using 1H NMR relaxation analysis. A summary of the good practice is presented

Single-sided magnets give hope that Nuclear Magnetic Resonance (NMR) might in future be used for in situ characterisation of hydration and water transport in the surface layers of concrete slabs. Towards that end, a portable NMR-MOUSE (MObile Universal Surface Explorer) has been used to follow the hydration of gypsum based plaster, a Portland cement paste and concrete mortar. The results compare favourably to those obtained using a standard laboratory bench-top spectrometer. Further, stray field imaging (STRAFI) based methods have been used with embedded NMR detector coils to study water transport across a mortar/topping interface. The measured signal amplitudes are found to correlate with varying sample conditions. (c) 2005 Elsevier Ltd. All rights reserved.

A new method of applying hydrophobic coatings to cement-based materials based on exposure to the treatment vapour is proposed. The method is demonstrated for the application of monomeric alkyl (isobutyl) alkoxy silane to cement paste and mortar samples manufactured and cured under a variety of conditions. The efficacy of the treatment is compared to conventional flood coating using magnetic resonance imaging (specifically SPRITE) to monitor the time dependent uptake of water into treated samples. It is concluded that the method as proposed is of significant benefit for some of the samples.

The nanoscale morphology of, and pore water interactions in, calcium silicate hydrate (C-S-H), the active component of cement, remain uncertain. H nuclear magnetic resonance (NMR) can fully characterize the nanoporosity of C-S-H in as-prepared material without the need for damaging sample drying. We use NMR to follow the density of C-S-H in sealed cured pastes as a function of degree of hydration (α) and water to cement ratio. We show clear evidence for C-S-H densification. The C-S-H "solid" density, exclusive of gel pore water, slightly decreases from ρ = 2.73 g/cm at α ≈ 0.4 to 2.65 g/cmat α ≈ 0.9 due to an increase in the number of layers in the nanocrystalline aggregates. In the same range, the C-S-H "bulk" density, including gel water, increases from around 1.8 to 2.1 g/cm. The increase corresponds to a transition from growth of low-density product containing gel pores to higher density product devoid of gel pores. We update Powers' classical model from 1947. In contrast to the single "hydrate" of Powers, NMR differentiates between C-S-H and calcium hydroxide and separates out the interlayer water within the C-S-H. It shows a clear nonlinearity in the growth of the different fractions with α. © 2012 American Chemical Society.

The loss of optical transparency when polymer films are immersed in water, which is called “water whitening,” severely limits their use as clear barrier coatings. It is found that this problem is particularly acute in films deposited from polymers synthesized via emulsion polymerization using surfactants. Water whitening is less severe in secondary dispersion polymers, which are made by dispersing solution polymers in water without the use of surfactants. NMR relaxometry in combination with optical transmission analysis and electron microscopy reveal that some of the water sorbed in emulsion polymer films is contained within nano-sized “pockets” or bubbles that scatter light. In contrast, the water in secondary dispersion polymer films is mainly confined at particle interfaces, where it scatters light less strongly and its molecular mobility is reduced. The addition of surfactant to a secondary dispersion creates a periodic structure that displays a stop band in the optical transmission. The total amount of sorbed water is not a good indicator of polymers prone to water whitening. Instead, the particular locations of the water within the film must be considered. Both the amount of water and the size of the local water regions (as are probed by NMR relaxometry) are found to determine water whitening.

Fast-field-cycling nuclear magnetic resonance (FFC-NMR) is a powerful technique for non-destructively probing the properties of fluids contained within the pores of porous materials. FFC-NMR measures the spin–lattice relaxation rate R1(f) as a function of NMR frequency f over the kHz to MHz range. The shape and magnitude of the R1(f) dispersion curve is exquisitely sensitive to the relative motion of pairs of spins over time scales of picoseconds to microseconds. To extract information on the nano-scale dynamics of spins, it is necessary to identify a model that describes the relative motion of pairs of spins, to translate the model dynamics to a prediction of R1(f) and then to fit to the experimental dispersion. The principles underpinning one such model, the 3τ model, are described here. We present a new fitting package using the 3τ model, called 3TM, that allows users to achieve excellent fits to experimental relaxation rates over the full frequency range to yield five material properties and much additional derived information. 3TM is demonstrated on historic data for mortar and plaster paste samples.

The results of one- and two-dimensional 1H nuclear magnetic resonance (NMR) pulsed field gradient (PFG) diffusometry studies of water in white cement paste with a water-to-cement ratio 0.4 and aged from 1 day to 1 year are reported. The study shows that the NMR PFG method is primarily sensitive to the capillary porosity. Data is fit on the basis of a lognormal pore size distribution with pore size dependent relaxation times. The volume mean capillary pore size is 4.2 μm in mature paste, similar to 1 week suggesting that hydrates and gel porosity do not form in the capillary porosity once the latter has been substantially created. No evidence is found of capillary pore anisotropy in cement paste.

© 2015, TELFORD. All rights reserved. GARField nuclear magnetic resonance (NMR) profiling is used to demonstrate that the sharp colour change boundary commonly used to locate the water front in cement and concrete capillary absorption tests is a poor indicator of the true depth of water penetration. Across a range of mortars and concretes, NMR invariably shows a smooth and often nearzero gradient in the degree of saturation at this boundary. Any sharp front that does exist, as might arise from a strong dependence of the effective diffusivity on concentration and a multi-modal pore size distribution on the nanoscale, is always far beyond the colour change line.

H NMR has been used to characterise white Portland cement paste incorporating 10 wt.% of silica fume. Samples were measured sealed throughout the hydration without sample drying. Paste compositions and C-S-H characteristics are calculated based on H NMR signal intensities and relaxation analysis. The results are compared with a similar study of plain white cement paste. While the presence of silica fume has little influence on C-S-H densities, the chemical composition is impacted. After 28 days of sealed hydration, the Ca/(Si + Al) ratio of the C-S-H is 1.33 and the H2O(Si + Al) ratio is 1.10 when 10% of silica fume is added to the white cement. A densification of the C-S-H with time is observed. There are no major changes in capillary, C-S-H gel and interlayer pore sizes for the paste containing silica fume compared to the plain white cement paste. However, the gel/interlayer water ratio increases in the silica fume blend.

H nuclear magnetic resonance has been applied to cement pastes, and in particular calcium silicate hydrate (C-S-H), for the characterisation of porosity and pore water interactions for over three decades. However, there is now renewed interest in the method, given that it has been shown to be non-invasive, non-destructive and fully quantitative. It is possible to make measurements of pore size distribution, specific surface area, C-S-H density and water fraction and water dynamics over 6 orders of magnitude from nano- to milli-seconds. This information comes in easily applied experiments that are increasingly well understood, on widely available equipment. This contribution describes the basic experiments for a cement audience new to the field and reviews three decades of work. It concludes with a summary of the current state of understanding of cement pore morphology from the perspective of H NMR. © 2013 Elsevier Ltd. All rights reserved.

This paper addresses some practical questions regarding the influence of hydrophobic treatments on the movement of water in sandstone. The broad line gradient echo magnetic resonance imaging technique has been used for monitoring the depth of penetration of alkyl alkoxysilane treatment into untreated sandstone and subsequently to visualise the movement and spatial distribution profile of water in the untreated and silane treated sandstone matrix. The experimental results show that the effect of hyrdrophobic treatment depends on whether the stone is in short-term or prolonged contact with water. For short term exposure, the presence of a silane treatment prevents the movement of water into and out of the sandstone matrix. However, after continuous long-term contact with water the hydrophobic treatment is unable to prevent the ingress and internal redistribution of water. The ability of water to infiltrate treated regions of sandstone has significant practical implication for stone structures where deterioration may be due to outward movement of water from the interior to the surface of the stone matrix.

This Guide is an introduction to the basic concepts of using 1H nuclear magnetic resonance (NMR) relaxometry to determine the state of water in cement, and hence the degree of cure of the cement and the cement microstructure, in particular the porosity. The Guide provides information on calibrating the equipment, the NMR responses that can typically be found from cement and on how to quantify the information obtained. Recommendations are made for the specification of suitable equipment, the set-up procedures required, and the experiments to be performed. Detailed results of an international round robin are included to demonstrate the usability, repeatability and accuracy of the method. The preparation of suitable non-cementitious reference materials is discussed.

Nuclear magnetic resonance (NMR) relaxation experimentation is an e ective technique for non-destructively probing the dynamics of proton-bearing uids in porous media. The frequencydependent relaxation rate T−1 1 can yield a wealth of information on the uid dynamics within the pore provided data can be t to a suitable spin di usion model. A spin di usion model yields the dipolar correlation function G(t) describing the relative translational motion of pairs of 1H spins which then can be Fourier transformed to yield T−1 1 . G(t) for spins con ned to a quasi-two-dimensional (Q2D) pore of thickness h is determined using theoretical and Monte Carlo techniques. G(t) shows a transition from three- to two-dimensional (2D) motion with the transition time proportional to h2. T−1 1 is found to be independent of frequency over the range 0.01{100 MHz provided h ? 5 nm and increases with decreasing frequency and decreasing h for pores of thickness h < 3 nm. T−1 1 increases linearly with the bulk water di usion correlation time b allowing a simple and direct estimate of the bulk water di usion coe cient from the high-frequency limit of T−1 1 dispersion measurements in systems where the in uence of paramagnetic impurities is negligible. Monte Carlo simulations of hydrated Q2D pores are executed for a range of surfaceto- bulk desorption rates for a thin pore. G(t) is found to decorrelate when spins move from the surface to the bulk, display three-dimensional properties at intermediate times and nally show a bulk-mediated surface di usion (L evy) mechanism at longer times. The results may be used to interpret NMR relaxation rates in hydrated porous systems in which the paramagnetic impurity density is negligible.

A model linking the molecular-scale dynamics of fluids confined to nano-pores to nuclear magnetic resonance (NMR) relaxation rates is proposed. The model is used to re-analyse fast field-cycling spin-lattice relaxation rate measurements for the separate water and oil dispersions from an oil-bearing shale [Korb et al., J. Phys. Chem. C, 118, 199 (2014)]. The model assumes that pore fluid can be characterized by three time constants: the surface and bulk diffusion correlation times and a surface desorption time constant. Results are shown to yield meaningful and consistent intra-pore dynamical time constants, insight into diffusion mechanisms and pore morphology. The shale is found to be oil-wetting and the water dispersion is found to be due to the interaction of aqueous Mn2+ ions with bulk water spins. Clay, mortar and plaster paste dispersions measurements have also been successfully re-analysed and a summary of the results is presented. The results demonstrate the wide applicability of the model which advances NMR dispersion experimentation as a powerful tool for measuring nano-porous fluid properties.

We discuss the effect of paramagnetic impurity content (thought to be predominantly Fe3+) in cement pastes on the interpretation of 1H NMR T2–T2 exchange spectra. Through measurements on synthesised C–S–Hwith greatly reduced paramagnetic impurity concentration, we show that the spectra cannot be explained by exchange between regions of different Fe3+ concentration but rather are explained by exchange between regions of different pore size.

Fast-field-cycling nuclear-magnetic-resonance (FFC NMR) experimentation measures the spin-lattice relaxation rate T1−1=R1 as a function of NMR frequency f. It is a proven technique for probing the nanoscale dynamics of H1 spins over multiple timescales. In many porous systems, fluid is confined to quasi-zero-dimensional (closed), quasi-one-dimensional (channel), or quasi-two-dimensional (planar) pores. Expressions are presented for R1(f) providing simulated dispersion curves for closed, channel, and planar pores where relaxation is associated with fluid movement relative to fixed relaxation centers in the solid. It is shown that fluid confined to nanosized (1–5 nm) spaces can be identified by submillisecond relaxation times for any geometry. The shape and magnitude of R1(f) is shown to be sensitive to pore geometry at low frequency only if relaxation is dominated by the motion of pore bulk fluid. Relaxation in most porous material is dominated by slow-moving surface fluid. Here, the pore geometry can only be distinguished if the relaxation center density is known a priori and then only at very low frequency. Systems containing mixtures of closed, channel, and planar pores of similar characteristic dimension h would present as three peaks at low frequency with closed pores providing the largest R1 and planar pores the smallest. Pore size and shape variability in real systems is shown to diminish the ability to distinguish the three peaks. We show that the ratio T1/T2, where T2 is the spin-spin relaxation time, is a complex function of h, the surface diffusion time constant τℓ, and NMR frequency for f>1 MHz. It is shown that measurements of T1/T2 at 20 MHz in cement paste and hydrocarbon rock capture information on both τℓ and h.

Nuclear magnetic resonance (NMR) relaxation experimentation is an effective technique for probing the dynamics of proton spins in porous media, but interpretation requires the application of appropriate spin-diffusion models. Molecular dynamics (MD) simulations of porous silicate-based systems containing a quasi-two-dimensional water-filled pore are presented. The MD simulations suggest that the residency time of the water on the pore surface is in the range 0.03-12 ns, typically 2-5 orders of magnitude less than values determined from fits to experimental NMR measurements using the established surface-layer (SL) diffusion models of Korb and co-workers [Phys. Rev. E 56, 1934 (1997)]. Instead, MD identifies four distinct water layers in a tobermorite-based pore containing surface Ca2+ ions. Three highly structured water layers exist within 1 nm of the surface and the central region of the pore contains a homogeneous region of bulklike water. These regions are referred to as layer 1 and 2 (L1, L2), transition layer (TL), and bulk (B), respectively. Guided by the MD simulations, a two-layer (2L) spin-diffusion NMR relaxation model is proposed comprising two two-dimensional layers of slow- and fast-moving water associated with L2 and layers TL+B, respectively. The 2L model provides an improved fit to NMR relaxation times obtained from cementitious material compared to the SL model, yields diffusion correlation times in the range 18-75 ns and 28-40 ps in good agreement with MD, and resolves the surface residency time discrepancy. The 2L model, coupled with NMR relaxation experimentation, provides a simple yet powerful method of characterizing the dynamical properties of proton-bearing porous silicate-based systems such as porous glasses, cementitious materials, and oil-bearing rocks.

1H nuclear magnetic resonance (NMR) relaxation analysis of water in progressively dried white cement paste is used to estimate the width and relative specific area of intra-C–S–H sheet pores and inter-C–S–H particle gel pores. The measurement is based on the ratio of solid echo to free induction decay signal amplitudes and the observation that as water is removed, so the surface fraction contributing to the solid echo increases. The intra- and inter-C–S–H pores are found to be 1.5 nm and 4.1 nm thick respectively. The total specific area and volume ratio is 2.4 and 0.88 respectively. The volume ratio of readily evaporable water within the pore types is 0.63. Hence, the sheet porosity is 47% of the total or 38% if based solely on evaporable water. The method is distinct from NMR analyses based on the relaxation time. There is good agreement between the measured widths by the two methods.

The link between anomalous water sorption and dynamic porosity in cement pastes is explored using spatially resolved GARField 1H nuclear magnetic resonance (NMR) relaxation analysis. A model is developed in which the effective capillary diffusion coefficient is dependent on the instantaneous pore size distribution. This and earlier data show changes in pore size distribution resultant from changes in saturation that do not occur instantaneously with changes in degree of saturation. Therefore, it is assumed that the pore size distribution is always relaxing exponentially towards a (saturation de pendent) equilibrium. It follows that the diffusivity is sample history (i.e.time) dependent as well as saturation dependent. This is sufficient to ex plain anomalies in rapid capillary water sorption. The same concepts are applied to slow drying. In this case, porosity changes occur on a timescale much shorter than drying so the system is always in dynamic equilibrium and anomalies are therefore not seen.

We present preliminary results of the first NMR T(1)-T(2) two-dimensional relaxation Correlation experiments performed using a one-sided NMR system in cement based materials. Two-dimensional correlation relaxometry has itself only recently been demonstrated in cement paste where it proved to be a particularly sensitive probe of pore-water dynamics providing direct information on exchange of water between the gel and capillary pore networks. Further to this we have observed differences in the structural development of a selection of cement pastes throughout the early stages of hydration and verified the theoretical frequency dependence of the ratio T(1)/ T(2). When coupled with instrumentation developments in one-sided NMR magnets the way is opened to detailed, spatially resolved studies of the development of hydration and porosity in the surface layers (top 50 mm) of cementitious materials. A new magnet, suitable for such applications, is discussed. (C) 2006 Elsevier Ltd. All rights reserved.

The results of a 1H double-quantum-filtered (DQF) nuclear magnetic resonance (NMR) study of water in cement pastes are reported. It is shown that the DQF signal increases with curing time and in sympathy with the loss of mobile single-quantum signal, suggesting strongly that a signal from 1H in chemically combined and strongly confined water is selectively observed. The DQF signal in white cement comprises at least two components: the first is assigned to portlandite (Ca(OH)2); the second is assigned to water in the planar, nanometre-wide, calcium–silicate–hydrate (C–S–H) gel pores. The pore water signal is significantly broader than that expected for bound water. The width is interpreted in terms of the water undergoing a two-dimensional walk in the vicinity of Fe3+ impurities. A simple model is presented and found to be consistent with experiment and the known Fe3+ concentration. In grey cements, a third component is identified and associated with Fe-rich phases. The analysis places a lower bound on the lateral extent of planar C–S–H pores. The change in DQF signal components upon drying a sample mirrors the loss of the singlequantum components observed in a parallel study.

It is shown that a combination of pulsed-field-gradient spin-echo ~PGSE! nuclear-magnetic-resonance~NMR! restricted diffusion analysis and NMR imaging may be used to measure the spatial dependence of the droplet size distribution in the cream layer of turbid oil-in-water emulsions. 1H-13C cyclic J cross-polarization PGSE is introduced as a technique for this purpose in cases where selective observation of the oil component ~or other carbohydrate constituent! is required. With this method, 13C nuclei are chemical shift selectively excited by cross-polarization from coupled 1H partners. An optimum detection sensitivity is ensured by transferring the polarization back to the coupled protons with which the combined imaging and diffusion experiment is then carried out. The spatial dependence of the oil droplet size distribution was measured for a series of emulsions containing various fractions of gum xanthan thickener dissolved in the water. The experimental results are compared with a recent model of the creaming process due to Pinfield, Dickinson, and Povey @J. Colloid Interface Sci. 166, 363 ~1994!#. When no gum xanthan is present, the experimental results are in good agreement with the model. However, the model fails to describe the droplet distribution for emulsions with a gum xanthan concentration of the order of 0.1 wt %. The discrepancy is discussed in terms of depletion flocculation and depletion stabilization.

H nuclear magnetic resonance (NMR), supported by a measurement of the degree of hydration using X-ray diffraction, has been used to fully characterise the nano-scale porosity and composition of calcium-silicate-hydrate (C-S-H), the active component of cement. The resultant "solid" density and composition are ρ = 2.68 g/cm; (Ca). (Si,Al)O. (HO) for an underwater cured, never-dried cement paste with an initial mix water-to-cement ratio of 0.4 after 28 days of hydration. In addition, the first pore-type resolved desorption isotherm of cement that shows the location of water as a function of relative humidity has been measured. Critical to our results is verification of the assignment of the different NMR spin-spin relaxation time components. These have been corroborated with conventional analyses. The new methodology is key to enabling design of cement pastes with lower environmental impact.

Changes of water state within the pore structure of cement paste due to temperature changes are followed by means of 1H-proton nuclear magnetic resonance (NMR) relaxation analysis. The study shows that with increasing temperature, the signal due to water contained in the smallest C-S-H interlayer spaces decreases while that from the larger gel pores, and to a lesser extent from the capillary pores, increases. On cooling, the opposite behavior is observed with complete reversibility. The observed changes in water populations appear to be instantaneous compared to the rate of temperature change in the samples. These changes are postulated to be responsible for macroscopically observed changes of relative humidity in pores during heating/cooling and are therefore key in understanding thermal deformations of cement based materials. It is evident that the previous hypothesis of microstructural delayed water transport being responsible for macrostructural delayed thermal deformations can be rejected. Different microstructural mechanisms are discussed that could explain the redistribution in water signals, namely water migration and pore rearrangement mechanisms.

The mobility of water within the microstructure of hardened cement paste has been at the center of a long-lasting debate, motivated by the need to understand the fundamental mechanisms that play a role in drying, shrinkage, creep and thermal expansion. Our 1H NMR results show for the first time that externally-applied pressure can lead to migration of water within the microstructure (microdiffusion). Upon compression, the gel water signal decreases. For the most part, this is accommodated by a corresponding increase in the signal of water in larger, interhydrate and capillary spaces. However, there is also an increase in the signal corresponding to the water in most confined spaces. Normally such tiny spaces are classified as hydrate interlayers. However, we do not conclude that there is a significant increase in interlayer water. Rather we attribute this part of the increase to a rearrangement of the microstructure upon compression with some water confined in increasingly small gel pore spaces. These findings show that the deformability of the microstructure (C-S-H gel) at the expense of gel porosity may explain part of the macroscopic deformations due to short-term creep.

A Brownian shell model describing the random rotational motion of a spherical shell of uniform particle density is presented and validated by molecular dynamics simulations. The model is applied to proton spin rotation in aqueous paramagnetic ion complexes to yield an expression for the Larmor-frequency-dependent nuclear magnetic resonance spin-lattice relaxation rate T1-1(co) describing the dipolar coupling of the nuclear spin of the proton with the electronic spin of the ion. The Brownian shell model provides a significant enhancement to existing particle-particle dipolar models without added complexity, allowing fits to experimental T-1 1(co) dispersion curves without arbitrary scaling parameters. The model is successfully applied to measurements of T -1 1 (co) from aqueous manganese(II), iron(III), and copper(II) systems where the scalar coupling contribution is known to be small. Appropriate combinations of Brownian shell and translational diffusion models, representing the inner and outer sphere relaxation contributions, respectively, are shown to provide excellent fits. Quantitative fits are obtained to the full dispersion curve of each aquoion with just five fit parameters, with the distance and time parameters each taking a physically justifiable numerical value.

We describe the development of in vivo one-dimensional MRI (profiling) using a GARField (Gradient At Right angles to Field) magnet for the characterisation of side-of-hand human skin. For the first time and in vivo, we report measurements of the NMR longitudinal and transverse relaxation parameters and self-diffusivity of the upper layers of human skin with a nominal spatial resolution better than 10 µm. The results are correlated with in vivo confocal Raman spectroscopy measurements of water concentration and natural moisturiser factors, and discussed in terms of known skin biology and microstructure of the stratum corneum and viable epidermis. The application of model moisturiser solutions to the skin is followed and their dynamics of ingress are characterised using the MRI methodology developed. Selected hydrophilic and lipophilic formulations are studied. The results are corroborated by standard in vivo measurements of transepidermal water loss and hydration status. A further insight into moisturisation mechanisms is gained. The effect of two different penetration enhancers on a commonly used skin care oil is also discussed, and different timescales of oil penetration into the skin are reported depending on the type of enhancer.

We describe a lattice Boltzmann modelling framework for fluid sorption coupled to a dynamic model of cement hydrate microstructure upon which it is possible to explore ideas of water sorption in cement emergent from NMR and other recent experimental studies. The results of the first simulations using the model are presented. We show that it is possible to extract transport and microstructural relaxation parameters from the simulations that are in good qualitative agreement with experiment. We discuss limitations of the methodology.

We use 1H nuclear magnetic resonance (NMR) methods to show that the relaxation time governing the redistribution of the gel-pore porosity in cement pastes during sorption depends, not surprisingly, on the dry state saturation and also, more surprisingly, on the sample size. The relaxation time is typically in the range 20 to 40 h for cylindrical samples 60 mm long dried to saturations between about 40 and 55%. It increases up to 200 h for samples dried to between 20 and 30% saturation. The times are all very much longer than for 1 mm samples. There is additional evidence to support the idea that the relaxation of hydrate inter-layer sized spaces occurs on at least two timescales, one of which is very much longer (months) than any of those listed above.

This paper demonstrates a model of softwood geometry that can be used for multiscale modelling of the longitudinal movement of water through spruce wood. Previous results obtained from a high resolution X-ray CT scan and subsequent image analysis of a large number of Norway spruce tracheids were here used to produce a model that can represent the variability in wood anatomy found within a timber joist or log. A demonstration of that model is given.

It is shown that broad line gradient echo magnetic resonance imaging is an ideal tool with which to study the ingress of hydrophobic polymer surface treatments into porous building materials, specifically in this case sandstone. It is further shown that the method can be used to quantitatively visualize the movement of water into and through the treated material, both from the surface and bulk, as a function of time. The influence of treatment cure time, cure temperature and substrate hydration on the subsequent water transport have been investigated. For the first time direct evidence of water pumping through a treated surface is presented.

Building on the legacy of the Sloan Digital Sky Survey (SDSS-I and II), SDSS-III is a program of four spectroscopic surveys on three scientific themes: dark energy and cosmological parameters, the history and structure of the Milky Way, and the population of giant planets around other stars. In keeping with SDSS tradition, SDSS-III will provide regular public releases of all its data, beginning with SDSS DR8 (which occurred in Jan 2011). This paper presents an overview of the four SDSS-III surveys. BOSS will measure redshifts of 1.5 million massive galaxies and Lya forest spectra of 150,000 quasars, using the BAO feature of large scale structure to obtain percent-level determinations of the distance scale and Hubble expansion rate at z100 per resolution element), H-band (1.51-1.70 micron) spectra of 10^5 evolved, late-type stars, measuring separate abundances for ~15 elements per star and creating the first high-precision spectroscopic survey of all Galactic stellar populations (bulge, bar, disks, halo) with a uniform set of stellar tracers and spectral diagnostics. MARVELS will monitor radial velocities of more than 8000 FGK stars with the sensitivity and cadence (10-40 m/s, ~24 visits per star) needed to detect giant planets with periods up to two years, providing an unprecedented data set for understanding the formation and dynamical evolution of giant planet systems. (Abridged)

Nuclear magnetic resonance (NMR) spin-lattice (T−1 1 ) and spin-spin (T−1 2 ) relaxation rate mea- surements can act as e ective non-destructive probes of the nano-scale dynamics of 1H spins in porous media. In particular, fast- eld-cycling T−1 1 dispersion measurements contain information on the dynamics of di using spins over time scales spanning many orders of magnitude. Previously- published experimental T−1 1 dispersions from a plaster paste, synthetic saponite, mortar and oil- bearing shale are re-analysed using a model and associated theory which describe the relaxation rate contributions due to the interaction between spins ensembles in quasi-two-dimensional (Q2D) pores. Application of the model yields physically-meaningful di usion correlation times for all systems. In particular, the surface di usion correlation time and the surface desorption time take similar values for each system suggesting that surface mobility and desorption are linked processes. The bulk uid di usion correlation time is found to be 2-5 times the value for the pure liquid at room temperature for each system. Re-analysis of the oil-bearing shale yields di usion time constants for both the oil and water constituents. The shale is found to be oil-wetting and the water T−1 1 dispersion is found to be associated with aqueous Mn2+ paramagnetic impurites in the bulk water. These results escalate the NMR T−1 1 dispersion measurement technique as the primary probe of molecular-scale dynamics in porous media yielding di usion parameters and a wealth of information on pore morphology.

The combination of the lattice Boltzmann Shan-Chen pseudo-potential method for multiphase fluids (Shan and Chen 1993 Phys. Rev. E 47 1815) and a grey or partial bounce back lattice Boltzmann algorithm for effective media (Walsh et al 2009 Comput. Geosci. 35 1186), is demonstrated for application to liquid-vapour fluid dynamics in porous media with porosity spanning a very wide range of length scales. Liquid / vapour distributions in cellular like structures with cell walls of reduced permeability are seen to follow expectation

The relative humidity (RH) dependence of the water permeability of cement is calculated from the water concentration profile of a paste exposed to an RH gradient and the desorption isotherm. The profile is measured using GARField, standing for Gradient at Right Angles to Field, NMR. The isotherm is derived from other earlier NMR measurements. The Darcy equation gives the intrinsic permeability as 4.6 × 10 m. The apparent intrinsic permeability to water flow shows a broad "U" shape dependence on RH, with a minimum of 7 × 10 m at RH 55%. The "U" shape is attributed to the fact that the transport mechanism involves a coupling of liquid and vapour modes. The data is further analysed in terms of a model of coupled liquid and vapour diffusion and Darcy flow due to Baroghel-Bouny et al. (Cem. Concr. Res. 2011 41 828) from which the relative liquid water and vapour permeabilities are calculated. They are strongly RH dependent. The former increases with increasing RH; the latter decreases. © 2013 Elsevier Ltd.

The first systematic study of the temporal evolution of the pore-size-distribution (PSD) in mature cement pastes following one and two cycles of drying and rewetting is presented. The PSD is measured using 1H nuclear magnetic resonance (NMR) relaxometry. For millimetre sized paste samples dried fairly strongly, the volume of water taken up shortly after rewetting slightly exceeds the pre-drying amount. The volume of water in pores > 10 nm far exceeds that in smaller pores. This reverses the situation observed prior to drying. Over subsequent days the water distribution reverts to its original form, so that the dominant fraction is again in the smaller pores. Since the total water content scarcely changes, this indicates a re-arrangement of the nano-scale porosity. Over two drying–rewetting cycles, both reversible and irreversible changes are seen. The effect is not observed in moderately dried pastes.

A new, portable NMR magnet with a tailored magnetic field profile and a complementary radio frequency sensor have been designed and constructed for the purpose of probing in situ the sub-surface porosity of cement based materials in the built environment. The magnet is a one sided device akin to a large NMR-MOUSE with the additional design specification of planes of constant field strength vertical bar B(0)vertical bar parallel to the surface. There is a strong gradient G in the field strength perpendicular to these planes. As with earlier GARField magnets, the ratio G/vertical bar B(0)vertical bar is a system constant although the method of achieving this condition is substantially different. The new magnet as constructed is able to detect signals 50 mm ((1)H NMR at 3.2 MHz) away from the surface of the magnet and can profile the surface layers of large samples to a depth of 35-40 mm by moving the magnet, and hence the resonant plane of the polarising field, relative to the sample surface. The matching radio frequency excitation/detector coil has been designed to complement the static magnetic field such that the polarising B(0) and sensing B(1) fields are, in principal, everywhere orthogonal. Preliminary spatially resolved measurements are presented of cement based materials, including two-dimensional T(1)-T(2) relaxation correlation spectra. (c) 2007 Published by Elsevier Inc.

This paper describes results that combine Shan-Chen two-phase (liquid-vapour) and partial-bounce back (semi-permeable membrane) methods of Lattice Boltzmann numerical modelling of fluid dynamics in order to understand how bordered pits influence the drying and rewetting of wood. In addition, preliminary results that introduce pressure induced distortion are included.

We show how the measurement of proton nuclear magnetic spin-lattice relaxation as a function of magnetic field strength (and hence nuclear Larmor frequency) can provide reliable information on the microstructure (specific surface area and pore size distribution) throughout the progressive hydration of cement-based materials. We present in details the experimental and theoretical characteristic features of the relaxation dispersion to support an interpretation in terms of coupled solid-liquid relaxation at pore interfaces, surface diffusion, and nuclear paramagnetic relaxation. The measurement does not require any drying temperature modification and is sufficiently fast to be applied continuously during the progressive hydration of the material. Coupling this method with the standard proton nuclear spin relaxation and high resolution NMR allows us to follow the development of micro-scale texture within the material. (C) 2006 Elsevier Ltd. All rights reserved.

Different solid phases, important to cement paste hydration, are investigated with low-field benchtop 1H nuclear magnetic resonance (NMR). A combination of the well-established quadrature echo pulse sequence with variable pulse gap together with a T1 saturation recovery quadrature echo pulse sequence is used. The results illustrate the diversity in the 1H NMR relaxation behaviour of solid phases that prospects the differentiation in more complex materials. We propose a procedure to obtain quantified values of the solid compounds using these unique relaxation responses of solids, called finger print, and apply this technique to well-hydrated white and ordinary Portland cement paste. Based on the results, needs and ways for future improvements are discussed.

This paper presents the design of the 'Tree Hugger', an open access, transportable, 1.1MHz (1)H nuclear magnetic resonance imaging system for the in situ analysis of living trees in the forest. A unique construction employing NdFeB blocks embedded in a reinforced carbon fibre frame is used to achieve access up to 210mm and to allow the magnet to be transported. The magnet weighs 55kg. The feasibility of imaging living trees in situ using the 'Tree Hugger' is demonstrated. Correlations are drawn between NMR/MRI measurements and other indicators such as relative humidity, soil moisture and net solar radiation.

Improvement in the signal-to-noise ratio of Nuclear Magnetic Resonance (NMR) systems may be achieved either by increasing the signal amplitude or by decreasing the noise. The noise has multiple origins – not all of which are strictly “noise”: incoherent thermal noise originating in the probe and pre-amplifiers, probe ring down or acoustic noise and coherent externally broadcast radio frequency transmissions. The last cannot always be shielded in open access experiments. In this paper, we show that pulsed, low radio-frequency data communications are a significant source of broadcast interference. We explore two signal processing methods of de-noising short

One dimensional profiles of the concentration of water absorbed from vapour diffusing into compacted type 4A zeolite powder have been obtained by broadline NMR imaging. After an induction period of approximately 6 h, a region of full hydration advances linearly with time into the zeolite plug. This behaviour is typical of Case II diffusion. A simple numerical simulation gives good agreement with the experimental results.

The use of solid state NMR imaging in reservoir core applications has long been proposed. This paper describes the use of a simple, robust technique in the first such application. One- and two-dimensional images of the irreducible brine in a sandstone and carbonate reservoir core are demonstrated. The applicability of solid state NMR imaging to pore surface relaxation estimation is discussed.

The paper shows that it is possible to combine the free energy lattice Boltzmann approach to multi-phase modelling of fluids involving both liquid and vapour with the partial bounce back lattice Boltzmann approach to modelling effective media. Effective media models are designed to mimic the properties of porous materials with porosity much finer than the scale of the simulation lattice. In the partial bounce back approach, an effective media parameter or bounce back fraction controls fluid transport. In the combined model, a wetting potential is additionally introduced that controls the wetting properties of the fluid with respect to interfaces between free space (white nodes), effective media (grey nodes) and solids (black nodes). The use of the wetting potential combined with the bounce back parameter gives the model the ability to simulate transport and sorption of a wide range of fluid / material systems. Results for phase separation, permeability, contact angle and wicking in grey media are shown. Sorption is explored in small sections of model multi-scale porous systems to demonstrate two-step desorption, sorption hysteresis and the ink-bottle effect.

Two-dimensional nuclear magnetic resonance relaxation correlation studies of cement pastes have been performed on a unilateral magnet, the Surface GARField. Through these measurements, the hydration process can be observed by monitoring the evolution of porosity. Characteristic relaxation time distributions have been observed in different cement pastes: fresh white cement, prehydrated white cement and ordinary Portland cement. The observed T-1/T-2 ratio in these cements has been shown to agree with expectations based on high field values. (C)) 2007 Elsevier Inc. All rights reserved.

1H nuclear magnetic resonance (NMR) relaxometry, supported by X-Ray diffraction and thermogravimetric analysis, has been used to characterise microstructure of white cement pastes underwater cured at temperatures in the range 10°C to 60°C. As the temperature increases, so the C-S-H, capillary pore water and interhydrate pore water content all increase; the ettringite and gel pore water content decrease; and the Portlandite content stays constant. A non-linear increase in the C-S-H ‘solid’ and ‘bulk’ densities, that exclude and include gel pore water respectively, has been observed with the increase of temperature. This is accompanied by a decrease in C-S-H water content but no change in the Ca/(Si + Al) ratio. The increase in the C-S-H ‘solid’ density has been attributed to a decrease in the number of locally stacked C-S-H layers. The increase in the C-S-H ‘bulk’ density is additionally attributed to the decrease in the gel porosity.

The results of a magnetic resonance spin-spin relaxation analysis and broad-line magnetic resonance imaging (MRI) (gradient-echo and stray-held imaging) study of water and water transport in Portland cement pastes are presented. The effect of varying the cure conditions and the water to cement (w/c) ratio of the sample mix are discussed. The water sorptivity and the concentration dependence of the hydraulic diffusion coefficient are calculated for samples prepared with a 0.5 w/c ratio and, therefore, an open pore structure. In the case of 0.3 w/c ratio samples, little water transport is observed, and a closed pore structure is inferred. (C) 1998 Elsevier Science Inc.

This study aimed to define the variability in the microstructure of Norway spruce within an annual ring by examining differences between earlywood and latewood. In particular we were interested in obtaining new information on bordered pit occurrence and locations relative to tracheid ends, plus the lumina dimensions and longitudinal overlap of tracheids that collectively define the longitudinal hydraulic pathways. A stacked series of X-ray micro-CT scans of an annual ring of Norway spruce were made and stitched together longitudinally to form a three-dimensional volume. The imaging resolution was carefully chosen to capture both longitudinal and transverse anatomical details. Measurements of tracheid length; overlap; radial lumen diameter and bordered pit location were made semi-automatically using image analysis. The distribution of radial lumen diameter was used to define earlywood and latewood. Then bordered pit linear density and spatial distribution, tracheid length and overlap were analysed, presented and contrasted for earlywood and latewood. Further differences between earlywood and latewood were found only in bordered pit linear density. Clear trends in radial lumen diameter and pit linear density were observed with radial position within the growth ring. These results provide new information on the variability of the Norway spruce microstructure within an annual ring.

The uptake, partitioning, and release of ingredients such as water, oil, surfactant, and ions are important factors to understand and control in the design and manufacture of detergent and personal products. Although conventional pulse NMR (PNMR) spectroscopy continues to be used to analyse bulk molecular mobility and phase composition, more recently MR imaging techniques have created unique opportunities for gaining spatial information about these processes in ways that are noninvasive and potentially quantitative. This paper describes the evaluation of MRI and associated PNMR techniques to study transport in three relevant cases: ion diffusion (e.g., fluoride) in concentrated dispersions, oil transport through powders, and water ingress into porous powders (zeolite). Results are presented to illustrate the potential of multiple pulse and gradient echo MRI methods for dealing with the short T2 scenarios that represent a common problem in quantitative imaging of water in solid-containing composites involving, for instance, zeolite, or silica. Pore-size characterisation results are also presented.

A probability density function describing the angular evolution of a fixed-length atom-atom vector as a Lévy rotor is derived containing just two dynamical parameters: the Lévy parameter α and a rotational time constant τ. A Lévy parameter α

This chapter reviews the complex step of drying in the latex film formation process. Drying modes have a profound effect on drying rates and on the final properties of films, primarily through their influence on film morphology and the distribution of water-soluble species. Three distinct drying modes (acting separately, successively or together) can be defined, namely homogeneous drying (in which the water concentration remains uniform in the sample throughout the drying process), drying normal to the surface (where a dry layer of increasing thickness develops from the air surface of the latex coating); and lateral drying (where dry areas increase in size in a direction parallel to the substrate). Details are given on the current knowledge and understanding of these drying modes. The last section of the chapter considers the main parameters controlling the drying modes, i.e. thickness and geometric effects, the structure and rheology of the dispersion, particle viscoelasticity, and the overall rate of water loss.