Effect of the manufacturing process on Fiore Sardo PDO cheese microstructure by multi-frequency NMR relaxometry.

The quality of Fiore Sardo cheese, a traditional Italian dairy product, was analyzed by means of Multi-frequency Nuclear Magnetic (NMR) relaxometry. Specifically, ten cheese wheels were purchased from different production chains, either industrial (N = 5) or artisanal (N = 5) samples. The former came from large scale productions and the latter were produced by shepherds in small quantities and in very small dairy factories. A preliminary interlaboratory proficiency testing of Time Domain - NMR (TD-NMR, 20 MHz) relaxometry by five laboratories, consistently showed that product quality is significantly different in terms of molecular mobility according to their production chain (i.e. industrial or artisanal). More detailed information about cheese microstructure was obtained by Multi-frequency Fast Field Cycling NMR (FFC-NMR) at lower magnetic fields (0.01-10 MHz). According to the interpretative model adopted to describe FFC-NMR data, industrially processed cheeses showed a higher para-casein hydration, higher protein protons to water protons ratio and a higher disorder (lower fractal dimension df) than artisanal products. It is suggested that differences between artisanal and industrial cheeses generate from the processing steps preceding cheese maturation, and are clearly reflected in the visual appearance of cheeses. This study shows that NMR relaxometry techniques can successfully discriminate Fiore Sardo cheese from different production chains, and paves the way for their implementation in quality control practices of dairy products.

Dynamical surface affinity of diphasic liquids as a probe of wettability of multimodal porous media.

We introduce a method for estimating the wettability of rock/oil/brine systems using noninvasive in situ nuclear magnetic relaxation dispersion. This technique scans over a large range of applied magnetic fields and yields unique information about the extent to which a fluid is dynamically correlated with a solid rock surface. Unlike conventional transverse relaxation studies, this approach is a direct probe of the dynamical surface affinity of fluids. To quantify these features we introduce a microscopic dynamical surface affinity index which measures the dynamical correlation (i.e., the microscopic wettability) between the diffusive fluid and the fixed paramagnetic relaxation sources at the pore surfaces. We apply this method to carbonate reservoir rocks which are known to hold about two thirds of the world's oil reserves. Although this nondestructive method concerns here an application to rocks, it could be generalized as an in situ liquid/surface affinity indicator for any multimodal porous medium including porous biological media.

Observation of exchange of micropore water in cement pastes by two-dimensional T(2)-T(2) nuclear magnetic resonance relaxometry.

The first detailed analysis of the two-dimensional (2D) NMR T(2)-T(2) exchange experiment with a period of magnetization storage between the two T(2) relaxation encoding periods (T(2)-store-T(2)) is presented. It is shown that this experiment has certain advantages over the T(1)-T(2) variant for the quantization of chemical exchange. New T(2)-store-T(2) 2D 1H NMR spectra of the pore water within white cement paste are presented. Based on these spectra, the exchange rate of water between the two smallest porosity reservoirs is estimated for the first time. It is found to be of the order of 5 ms{-1}. Further, a careful estimate of the pore sizes of these reservoirs is made. They are found to be of the order of 1.4 nm and 10-30 nm , respectively. A discussion of the results is developed in terms of possible calcium silicate hydrate products. A water diffusion coefficient inferred from the exchange rate and the cement particle size is found to compare favorably with the results of molecular-dynamics simulations to be found in the literature.

Microstructure evolution of hydrated cement pastes.

We propose an original method based on both proton nuclear magnetic relaxation dispersion and high-resolution NMR spectra to investigate the microstructure of synthesized Ca3SiO5-hydrated cement paste. This method allows a clear assessment of the local proton chemical sites as well as the determination of dynamical information of moving proton species in pores. We show also how the microstructure evolves during and after completion of hydration in a range of length scales between 2 and 500 nm. In particular, we show how the pore size distribution of the cement paste reaches progressively a power-law characteristic of a surface-fractal distribution with a dimension Df = 2.6, which takes into account the hierarchical order in the material. Last, we study how this pore size distribution is modified during setting by varying either the water-to-cement ratio or addition of ultrafine particles. This shows that our method could be relevant to relate the mechanical properties to the microstructure of the material. This proposed NMR method is general enough for the characterization of microstructure of any porous media with reactive surface involving water confinement.

Surface relaxation and chemical exchange in hydrating cement pastes: a two-dimensional NMR relaxation study.

We report the first nuclear magnetic resonance (NMR) two-dimensional correlation T(1) - T(2) and T(2) - T(2) measurements of hydrating cement pastes. A small but distinct cross peak in the two-dimensional relaxation spectrum provides the first direct evidence of chemical exchange of water between gel and capillary pores occurring over the first 14 days of hydration. A correlation of features along the line T(1) = 4T(2) provides strong supportive evidence for the surface diffusion model of (1)H nuclear spin relaxation in cements and for a multimodal discrete pore size distribution. Differences in detail of the results are reported for white cement paste and white cement paste with added silica fume. Both the method and the theory presented can be applied more widely to other high surface area materials with other reactive surface areas.

Universal nuclear spin relaxation and long-range order in nematics strongly confined in mass fractal silica gels.

We show how the low-frequency dependence of the proton spin-lattice relaxation time T1(nu) of octylcyanobiphenyl liquid crystals confined in high-density silica gels evidences a long-range order nematic phase in spite of the strong confinement and random disorder of the gels. The universal value and frequency dependence observed, T1(nu) proportional, variant nu(2/3), is interpreted within a relaxation model due to director fluctuations in nematic liquid crystals confined to mass fractal porous media. The model provides a relation T1(nu) proportional, variant nu(2-d/2), giving a reliable value of the structural fractal dimension d(f)=2.67 for all the host silica gels.

Surface nuclear magnetic relaxation and dynamics of water and oil in granular packings and rocks.

Low field proton nuclear spin-relaxation at variable magnetic field strength and temperature provides surface dynamical parameters such as surface diffusion coefficients, activation energies, time of residence and coefficient of surface affinity. These parameters were extracted from measurements on grain packs and natural oil-bearing rocks. On grain packs, we show first that changing the amount of surface paramagnetic impurities leads to striking different relationships between the pore-size and the relaxation times T1 and T2. These relationships are well supported by fast-diffusion (surface-limited) or slow-diffusion relaxation models. Surface relaxivity parameters rho1 and rho2 are deduced from the pore size dependence in the fast-diffusion regime. Then, we evidence the frequency and temperature dependence of the surface relaxivity rho1 by field cycling NMR relaxation and relevant theoretical models. The typical frequency dependence found allows an experimental separation of the surface and bulk microdynamics in granular packings and petroleum rocks and the determination of the above mentioned surface dynamical parameters. Finally, we present the first field cycling nuclear spin relaxation experiments performed in water/oil saturated petroleum rocks. We believe that these experiments give new information about the surface localization of these two saturating liquids in pores.

What is the surface specific area of porous cement-based material? A nuclear magnetic relaxation dispersion approach.

We propose a new NMR method to measure and follow the evolution of the surface specific area, Sp, of a porous cement-based material. This method, that does not require any preliminary drying process, uses nuclear magnetic relaxation dispersion (NMRD), the measurement of spin-lattice relaxation rate as a function of magnetic field strength or nuclear Larmor frequency. The method is applied for three different mortars samples prepared by mixing cement, sand, silica fume, water and superplasticizer with a water to cement ratio w/c=0.25, 0.38 and 0.65, respectively. The evolution of Sp grows linearly with the degree of advancement of chemical reactions measured by thermal heating and we evidence two relaxation processes independent of the w/c ratio.

Micropore size analysis by NMR in hydrated cement.

The understanding of the microstructure of cement remains incomplete. Especially, the progressive setting of the material is still unclear. Micropore size distribution (microstructure) has been investigated by both standard proton nuclear magnetic relaxation (1H-NMR) and field-cycling relaxation in C3S hydrated paste. The non-exponential decay was interpreted as a distribution of discrete relaxation rates. The attribution of T1 is supported by both a spectral and a dispersion curve analyses. These experiments allow us to follow the structuration of the material during setting.

Probing the surface area of a cement-based material by nuclear magnetic relaxation dispersion.

We show how nuclear magnetic spin-lattice relaxation dispersion of 1H water can provide a direct reliable value of the specific surface area of a cement-based material. The remarkable features of the relaxation dispersion support an interpretation in terms of coupled solid-liquid relaxation at pore interfaces, surface diffusion, and nuclear paramagnetic relaxation. The measurement is sufficiently fast to be applied continuously during the progressive hydration and setting of the material. This method is relevant to other chemically reactive porous media in chemical engineering and oil recovery.

Slow dynamics of embedded fluid in mesoscopic confining systems as probed by NMR relaxometry.

Mesoscopic media such as porous materials or colloidal dispersions strongly influence the dynamics of the embedded fluid. In the strong-adsorption regime, it was recently proposed that the effective surface diffusion on flat surface is anomalous and exhibits long-time pathology, enlarging the time domain of the embedded-fluid dynamics towards the low-frequency regime. An interesting way to probe such a slow interfacial process is to use the field-cycling NMR relaxometry. This technique is used here to probe the fluid dynamics in two types of interfacial systems: i) a colloidal glass made of thin and flat particles; ii) a fully saturated porous media, the Vycor glass. Experimental results are critically compared to either a simple theoretical model of NMR dispersion involving elementary steps of the fluid dynamics near an interface (loops, trains, tails) or Brownian-dynamics simulations performed inside 3D reconstructions of these confined systems.

Surface nuclear magnetic relaxation and dynamics of water and oil in macroporous media.

Proton nuclear spin-relaxation studies on water- or oil-saturated granular packings and limestone rocks allow estimating surface molecular dynamical parameters. Measurements were performed at various conditions of temperature, magnetic field strengths, and pore size. We show by low field NMR relaxation that changing the amount of surface paramagnetic impurities leads to striking different pore-size dependences of the relaxation times T1 and T2 of liquids in pores. These dependences are well supported by surface-limited or diffusion-limited relaxation models. Surface relaxivity parameters rho(1) and rho(2) are deduced from the pore-size dependence in the surface-limited regime. We evidence the frequency and temperature dependence of the surface relaxivity rho(1) by field cycling NMR relaxation and relevant theoretical models. The typical frequency dependence found allows an experimental separation of the surface and bulk microdynamics in porous media. Several surface dynamical parameters, such as diffusion coefficients, activation energies, time of residence, and coefficient of surface affinity, were therefore determined. The methods presented here give a powerful analysis of the surface microdynamics of confined liquids, which can be applied to the study of oil-bearing rocks.

Surface dynamics of liquids in porous media.

We report remarkable differences in the 1H nuclear magnetic relaxation dispersion data (NMRD) between water and other common aprotic solvents such as acetone when in contact with high surface area calibrated microporous chromatographic silica glasses that contain trace paramagnetic impurities located at or close to the pore surface. All these differences have been related to the particular chemical behaviors and dynamics of these liquids at the pore surface. We apply this technique to probe the structure and dynamics of water and oil at the surface of calibrated macroporous systems, where similar surface dynamics effects have been observed. This technique is also applied to follow the first hydration stage of a white cement-paste. Last, we present an analysis of the magnetic field dependence of 1H nuclear relaxation data to exhibit the microporosity of ultra high performance concretes.

New ways of probing surface nuclear relaxation and microdynamics of water and oil in porous media.

The microdynamics of water and oil in macroporous media with SiO2 or CaCO3 surfaces has been probed at various temperatures by magnetic field-cycling measurements of spin-lattice relaxation rates. These measurements and an original theory of surface diffusion allow us to obtain surface dynamical parameters such as surface correlation times, residence times and diffusion coefficients. A coefficient of affinity of the liquids for the pore surface is deduced.

Micropore size analysis in hydrated cement paste by NMR.

We present a time evolution of 1H spin-lattice relaxation rates in the laboratory (1/T(1)) and in the rotating frame (1/T(1rho)) of a synthetic cement paste. The typical results found for both rates allows us to follow the main hydration stages of the cement paste and the refinement of its microporosity. In particular the texturation of the porosity and the structuration of the surface of the material is evidenced.

Investigation of the microporosity of high performance concrete by proton nuclear relaxation.

The difference in microporosity features between high and ultra high performance concrete was highlighted by measuring their respective proton spin-lattice relaxation times. A surface fractal dimension was attributed to each formulation and exhibits a correlation with the amount of calcium silicate hydrates.

Anomalous surface diffusion of water compared to aprotic liquids in nanopores.

1H nuclear magnetic relaxation dispersion experiments show remarkable differences between water and acetone in contact with microporous glass surfaces containing trace paramagnetic impurities. Analyzed with surface relaxation theory on a model porous system, the data obtained for water show that proton surface diffusion limited by chemical exchange with the bulk phase permits long-range effectively one-dimensional exploration along the pores. This magnetic-field dependence coupled with the anomalous temperature dependence of the relaxation rates permits a direct interpretation in terms of the proton translational diffusion coefficient at the surface of the pores. A universal rescaling applied to these data collected for different pore sizes and on a large variety of frequencies and temperatures, supports this interpretation. The analysis demonstrates that acetone diffuses more slowly, which increases the apparent confinement and results in a two-dimensional model for the molecular dynamics close to surface relaxation sinks. Surface-enhanced water proton diffusion, however, permits the proton to explore a greater spatial extent of the pore, which results in an apparent one-dimensional model for the diffusive motions of the water that dominate nuclear spin relaxation.

Analysis of microporosity and setting of reactive powder concrete by proton nuclear relaxation.

The proton spin-lattice relaxation measured at several frequencies leads to a resolved distribution of four Tli for reactive powder concrete (RPC). The typical Tli frequency dependences are quantitatively interpreted by a biphasic fast exchange model and a proton nuclear relaxation of hydrated paramagnetic ions at the surface of the pores. This leads to an estimation of the pore sizes. We present the first application of this nuclear relaxation method to follow in situ the kinetics of the hydration and setting of such material.

Translational diffusion of liquids at surface of microporous materials: new theoretical analysis of field cycling magnetic relaxation measurements.

1H spin-lattice relaxation rates of several aprotic polar liquids on calibrated microporous chromatographic glass beads that have paramagnetic ion impurities are recorded over magnetic field strengths using a field-switched magnetic relaxation dispersion spectrometer. The typical bilogarithmic magnetic field dependence of these rates supports quantitatively our theory of nuclear paramagnetic relaxation and gives the translational diffusion at the surface of nanopores. Our results demonstrate that magnetic relaxation dispersion at low magnetic field strengths in high surface area heterogeneous systems may be quantitatively understood in terms of the parameters of the spatial confinement and the local translational dynamics.

Magnetic cross-relaxation and chemical exchange between microporous solid and mobile liquid phases.

Nuclear magnetic spin-lattice relaxation rates are reported as a function of magnetic field strength, pH, and temperature for water protons in Sephadex gels. The water proton rates report the relaxation profile characteristic of the solid at high pH values. At lower pH values, the relaxation rate is limited by a slow chemical exchange process that makes the relaxation rate independent of magnetic field at low field strengths. In cases where the proton exchange rate does not limit the total relaxation rate, the magnetic field dependence of the relaxation rate is given by a power law of the type R = Av-B, where B is 0.75 except at pH 11 where the data are better represented with B = 0.5. The exchange events important for the water proton relaxation are represented as a two-stage process in which water within the pores of the gel exchanges protons and magnetization with the solid spin system rapidly compared with the rate at which the water within the pores exchanges with the bulk water phase.