Low-field NMR Relaxation Research Articles

Mechanism analysis of rheological properties of 3D printed steel slag cementitious composite based on low field nuclear magnetic relaxation test

Rheological properties play a crucial role in characterizing 3D printed cement-based materials. To further investigate the mechanism behind rheological evolution, this study employs low-field NMR relaxation time measurement to characterize the microstructure evolution of 3D printed steel slag cementitious material within the first 6 hours. This is combined with rheological parameters to explore the relationship between the mixture's rheological properties and pore microstructure over time. The results demonstrate that relaxation time effectively represents the temporal characteristics of rheological parameters, while pore throat distribution (0–0.1μm) exhibits a positive correlation with plastic viscosity. Low-field NMR relaxation characteristics can effectively describe early properties of 3D printed cementitious materials and provide valuable data support for future exploration of non-destructive testing during early stages.

Investigating the behaviour of NaCl brines and hydrocarbons in porous alumina using low-field NMR relaxation and diffusion methods.

The behaviour of multiple fluid phases within a porous medium is hard to predict. NMR measurements offer an excellent tool to probe such systems in a fast and non-invasive way. Such systems can be relevant to hydrocarbon recovery, catalysis, and CO2 and H2 geo-storage, among others. Since electrolyte solutions are always present in subsurface reservoirs, understanding their behaviour within porous media is highly important. In this study, we use NMR relaxation and diffusion methods to investigate the diffusion coefficients and strength of interactions between alumina surfaces and brines at various NaCl concentrations, focusing on the effect of salt concentration on transport and interactions within the porous structure. Furthermore, we study the spontaneous displacement of dodecane, a model hydrocarbon, from the same alumina pellets using the same brine solutions. Results show that brines of lower salinity consistently displace more dodecane in total, after soaking dodecane-saturated pellets in a brine solution for several days. This indicates that increased salt concentrations can reduce wettability towards the aqueous phase in simple metal oxide surfaces and highlights the capabilities of NMR to efficiently study such systems.

Comparative analysis of vegetable oils by 1H NMR in low and high magnetic fields

High-resolution 1H NMR, high-field 1H NMR relaxometry, and low-field (<0.5 T) NMR relaxometry have been applied to study different types of olive and soybean oils. It has been shown that the use of spectral and relaxation information in high-field NMR is an effective tool for the detection of oil adulteration and identification of food oils, including oils with close content. We have also shown that low-field NMR relaxation measurements can be applied for the discrimination between various food oils in the case of a limited group of samples. This work has demonstrated the possibilities of the different types of pulse NMR experimental methods for the analysis of vegetable oils.

Low-field 2D NMR relaxation and DRIFTS studies of glucose isomerization in zeolite Y: New insights into adsorption effects on catalytic performance

Sn and Ga doped zeolite Y catalysts were tested for the isomerization of glucose to fructose carried out in different solvents (water, methanol and ethanol). Therein, ethanol favoured a Lewis acid site catalyzed pathway that promotes glucose isomerization to fructose, whereas methanol resulted in an equal distribution of products (mannose, fructose and alkyl fructoside). In contrast, the catalysts were totally inactive in water solvent. NMR relaxation measurements, including solvent displacement experiments, suggested that the lack of catalytic activity in water is due to the strong adsorption of this solvent within the zeolite pores blocking reactants from the Lewis acid sites active for the sugar isomerization. In comparison, ethanol adsorbs relatively more strongly than methanol, hence is retained in the pores where solvated fructose is preferentially prevented from the further reaction on Brønsted acid sites situated outside of the pore space. NMR relaxation measurements using pyridine and tetrahydrofuran (THF) and pyridine-DRIFTS measurements suggest metal doping had little effect on the overall relative acid strength of the zeolites but resulted in zeolites with increased Lewis acid strength relative to the non-doped zeolites. The results reported provide direct experimental evidence on the importance of adsorption properties of solvents within zeolites used for glucose to fructose isomerization and may serve as a starting point for a new approach towards designing and optimizing such catalytic systems.

Using low-field NMR relaxation to optimise particulate dispersions

Formulation of particulate dispersions is a difficult industrial problem, with a multitude of system details influencing the final outcome. Solvent relaxation NMR is shown to help optimise the formulation of particulate dispersions of a range of widely used commercial silicas. Solvent at the particle interface is sensitive to details of the formulation, and it is shown that the average solvent spin-relaxation time in a dispersion can be used to monitor wetted surface area, sample sedimentation, and additive amounts; chemical syntheses and mechanical degradation of silicas are also monitored to optimise the dispersions. The experiments, which can be carried out on bench-top or on-line spectrometers, are not limited to silicas and can be generalised to other particles in a range of aqueous and non-aqueous dispersions, providing useful feedback to the formulator anywhere surfactants, polymers, pH, ionic strength, Hamaker constants, and surface charge play a role in stabilisation. • Rapid NMR relaxation measurements reveal variation in silica surface chemistry. • Breakup of silica aggregates is monitored by NMR relaxation to optimise processing. • NMR relaxation measurements provide facile quality control tests for hydrogels. • Silica particle syntheses are monitored by NMR relaxation.

Assessment of meat quality distributions of breast fillets with woody breast condition in the raw and cooked state.

The objective of this study was to determine meat quality distributions and assess hardness distributions in raw and cooked breast fillets with the woody breast (WB) condition, in addition to evaluating the relationship between water properties and WB severity. A total of 90 breast fillets were collected and categorized as normal (NORM), mild (MILD) and severe (SEV). Breast weight, drip loss, compression measurements, cook loss, shear and texture profile analysis (TPA) values were measured for each sample by fillet location (cranial to caudal) and sampling depth (cranial-superficial, cranial-internal, middle-superficial, and middle-internal) in the raw and cooked meat state. Low-field NMR relaxation measurements were also collected for both the raw and cooked fillets. Results indicate that severe WB expressed increased hardness, a higher water content (bound water and free water) and reduced meat quality attributes in raw and cooked meat. Breast fillet hardness and meat quality distributions were unevenly distributed between fillets, compression measurements were higher mainly in the cranial region, and progressively decreased toward the caudal region for both raw and cooked fillets. Shear force and energy values were higher in the cranial region than in the middle region, and TPA values were higher in superficial regions rather than internal portions. Additionally, low-field NMR could be used to predict WB through variation in water properties as thermal processing reduces water distributing abilities in affected fillets.

Low-field and variable-field NMR relaxation studies of H2O and D2O molecular dynamics in articular cartilage.

Osteoarthritis (OA) as the main degenerative disease of articular cartilage in joints is accompanied by structural and compositional changes in the tissue. Degeneration is a consequence of a reduction of the amount of macromolecules, the so-called proteoglycans, and of a corresponding increase in water content, both leading to structural weakening of cartilage. NMR investigations of cartilage generally address only the relaxation properties of water. In this study, two-dimensional (T1-T2) measurements of bovine articular cartilage samples were carried out for different stages of hydration, complemented by molecular exchange with D2O and treatment by trypsin which simulates degeneration by OA. Two signal components were identified in all measurements, characterized by very different T2 which suggests liquid-like and solid-like dynamics. These measurements allow the quantification of separate hydrogen components and their assignment to defined physical pools which had been discussed repeatedly in the literature, i.e. bulk-like water and a combination of protein hydrogens and strongly bound water. The first determination of 2H relaxation dispersion in comparison to 1H dispersion suggests intramolecular interactions as the dominating source for the pronounced magnetic field dependence of the longitudinal relaxation time T1.

Proton Low Field NMR Relaxation Time Domain Sensor for Monitoring of Oxidation Stability of PUFA-Rich Oils and Emulsion Products.

The nutritional characteristics of fatty acid (FA) containing foods are strongly dependent on the FA’s chemical/morphological arrangements. Paradoxically the nutritional, health enhancing FA polyunsaturated fatty acids (PUFAs) are highly susceptible to oxidation into harmful toxic side products during food preparation and storage. Current analytical technologies are not effective in the facile characterization of both the morphological and chemical structures of PUFA domains within materials for monitoring the parameters affecting their oxidation and antioxidant efficacy. The present paper is a review of our work on the development and application of a proton low field NMR relaxation sensor (1H LF NMR) and signal to time domain (TD) spectra reconstruction for chemical and morphological characterization of PUFA-rich oils and their oil in water emulsions, for assessing their degree and susceptibility to oxidation and the efficacy of antioxidants. The NMR signals are energy relaxation signals generated by spin–lattice interactions (T1) and spin–spin interactions (T2). These signals are reconstructed into 1D (T1 or T2) and 2D graphics (T1 vs. T2) by an optimal primal-dual interior method using a convex objectives (PDCO) solver. This is a direct measurement on non-modified samples where the individual graph peaks correlate to structural domains within the bulk oil or its emulsions. The emulsions of this review include relatively complex PUFA-rich oleosome-oil bodies based on the aqueous extraction from linseed seeds with and without encapsulation of externally added oils such as fish oil. Potential applications are shown in identifying optimal health enhancing PUFA-rich food formulations with maximal stability against oxidation and the potential for on-line quality control during preparation and storage.

Melting of tetrahydrofuran hydrate in pores: An investigation by low-field NMR relaxation

Transverse relaxation times T2 spectra for models of thawing hydrate-bearing sediment have been studied in this work. The samples were prepared from aqueous THF solution and powders of quartz microspheres or their mixtures with kaolin. It was shown that individual bands in the spectra of T2 times are traced, they correspond to proton relaxation in solid hydrate, aqueous solution of THF and to a thin layer of liquid located at the boundary between hydrate and solid particles. It was experimentally established that the low-field NMR may be applied to study the formation/melting kinetics of THF hydrates in porous media and as a tool to investigate phase transformations in porous media.

Tailoring pore structure and surface chemistry of microporous Alumina-Carbon Molecular Sieve Membranes (Al-CMSMs) by altering carbonization temperature for optimal gas separation performance: An investigation using low-field NMR relaxation measurements

In this work, we applied low-field, NMR spin–lattice measurements to evaluate for the first time the effect of carbonization temperature (range 600–1000 ℃) on the preparation of Alumina-Carbon Molecular Sieve Membranes (Al-CMSMs), providing new insights into intra-pore fluid interactions. The results show that the average Al-CMSM pore size generally increases with carbonization temperature whilst the hydrophilicity of the pore surface, and the amount of strongly adsorbed H2O, decreases with an increasing carbonization temperature. As such, lower carbonization temperatures produce more hydrophilic membranes, with further evidence provided by FTIR measurements demonstrating the presence of polar functional groups on the surface, with water interacting more strongly with the membrane surface, as evidenced by NMR.It was found that the Al-CMSM carbonization temperature significantly affected permeance and H2O/CH4 permselectivity by altering the membrane pore size distribution and pore hydrophilicity. H2O permeance values are seen to be up to 100 times larger than respective CH4 permeance values. The greater permeance of H2O is attributed to the larger kinetic diameter of CH4 relative to H2O and the adsorption of water in the hydrophilic pores enhancing the adsorption-diffusion transport mechanism. Optimal water permeation temperatures are thus higher for the more hydrophilic membranes, obtained at lower carbonization temperatures, as more energy is required to remove strongly adsorbed water blocking the pores. At higher carbonization temperatures, the Knudsen diffusion mechanism of permeance dominates over the adsorption-diffusion mechanism thereby reducing permeance as diffusion slows due to collisions between gas molecules and the pore walls. CH4 permeation always occurs via Knudsen diffusion with CH4 permeance increasing with permeation temperature due to the increased rate of CH4 diffusion.

Transverse relaxation characteristic and stress relaxation model considering molecular chains of HTPB coating based on pre-strained thermal aging

In order to accurately describe the transverse relaxation characteristic and stress relaxation modulus of HTPB coating during pre-strain thermal aging process, a one month thermal aging test was carried out at 70 °C with pre-strain of 0%, 3%, 6% and 9%, respectively. The low-field 1H NMR and stress relaxation modulus tests were carried out for HTPB coating at different aging stages. The stress relaxation model considering the molecular chains was proposed according to the changes of crosslinking chain and dangling chain of HTPB coating during pre-strain aging. The results showed that with the increase of aging time, the decay rate of transverse relaxation curve became faster, the transverse relaxation time decreased, the value of combined parameter qMrl increased, the proportion of crosslinking chain decreased, while the proportion of dangling chain increased. Moreover, the stress relaxation modulus increased, the crosslinking network structure of HTPB coating became denser and the degree of crosslinking increased. At the initial aging stage, the pre-strain will destroy the crosslinking network structure of HTPB coating to a certain extent. With the increase of aging time, the effect of pre-strain will gradually weaken and the influence of aging on materials will gradually increase. The correlations between the stress relaxation model considering the molecular chains and the test results were more than 0.9950, which can accurately describe the stress relaxation modulus of HTPB coating during the pre-strain thermal aging process.

Formation of methane hydrate from water sorbed by anthracite: An investgation by low-field NMR relaxation

Transverse relaxation time spectra T2 were studied for the samples (a) of wet coal in which methane hydrate was obtained, (b) wet coal exposed under the pressure of methane without the formation of the hydrate, and (c) initial wet coal. In all these cases, the samples of wet coal contained only water adsorbed in the fine pores of the coal substance. It was demonstrated that hydrate formation and the competitive sorption of methane at the positions previously occupied by water causes replacement of a part of water from coal mesopores into larger pores. The data obtained confirm a previously proposed multistage model (Smirnov et al., 2018) of hydrate formation in natural coal, which includes the stages of replacement of a part of sorbed water from coal pores by gas, the formation of microscopic water fragments in larger coal pores, and the formation of hydrate from this water.

Low field NMR relaxation as a probe to study the effect of activators and retarders on the alkali-activated GGBFS setting process

Low field nuclear magnetic resonance relaxometry (LF-NMR) was used to study the setting process of alkali-activated GGBFS (AA-GGBFS) paste during the early curing hours. LF-NMR measurements were carried out from fresh paste casting until hardening (generally no more than 8 h). The transverse relaxation time T2 was used as a probe to assess the setting process. Combined with Vicat penetration and temperature monitoring, an important threshold indicator was defined as the deadline for paste casting (DPC). The physical meaning of the DPC is a threshold point where the developing micro pores make loss of movable water attain a certain level so that the semi-solid paste has slight strength. Moreover, several periods related to AA-GGBFS early-hour paste development are proposed: (1) dissolution; (2) setting; (3) acceleration; and (4) hardening. By analysing each period during the early hours, it was found that the hybrid retarder of zinc nitrate and sodium gluconate works for the AA-GGBFS system.

Effect of secondary heat-induced aggregation on pork meat batter protein conformation, hydration characteristics, textural quality and in vitro digestibility.

Secondary heating (SH, 30 min at 100 °C), which has a great influence on elastic gels, has been widely applied to emulsified meat products to extend their shelf life. The effects of SH on the textural and nutritional qualities, water migration of meat batter and on the conformations, aggregation and in vitro digestibility of the meat proteins were investigated. Various heat treatments were tested, and the results revealed that an initial heating at 75 °C yielded the highest low-field NMR relaxation time T22 and peak area P22 and the highest in vitro digestibility. As this initial heating time was increased, the α-helix content, water-holding capacity (WHC) and protein digestibility all decreased. Furthermore, SH yielded a much more obvious decrease in the pepsin activity on the protein digestibility than just the initial heating, and also yielded increases in β-sheet content, hardness, gumminess, and chewiness. This result implied that gel shrinkage and protein aggregation occurred, causing decreased WHC and protein digestibility. Also, SH resulted in significantly decreased (P < 0.05) intensities of myosin light chain gel electrophoresis bands. Therefore, SH was concluded to have reduced the textural quality and nutritional value of the meat.

Field-frequency lock approach for 21.3-MHz high-performance NMR relaxation analyzer

Low-field NMR (LF-NMR) relaxation analyzers have been more and more widely used in food science, biomedicine, and petroleum exploration in recent years. An LF-NMR device analyzes various interactions between sample molecules through spin relaxation, diffusion, flow, and imaging experiments. However, temporal field fluctuations in the magnet limit the scope of application. A stable magnetic field is the basic guarantee for detecting weak signals with shorter relaxation time. This paper presents an approach involving a field-frequency lock for a 21.3-MHz high-performance NMR bipolar permanent magnet. The diameter spherical volume (DSV) of the magnet is only 60 mm. The field-frequency lock system uses 19F in a micro coil integrated into the main probe as a lock detector. The required magnetic field compensation can be calculated from the lock free induction decay (FID) signal frequency, which is measured by lock spectroscopy. The compensation coils used to produce the magnetic field were designed based on Helmholtz coils. The system determines the signal frequency by detecting the lock FID signal and calculates the required compensation-coil current to stabilize the main magnetic field of the analyzer. The results of practical locking experiments in a 21.3-MHz high-performance NMR relaxation analyzer showed that this new approach helps to reduce magnetic field fluctuations from 11 ppm/3h (11 × 10–6) to 0.4 ppm/3h (0.4 × 10–6), which meets the application requirements. This approach is especially viable and effective for a permanent magnet with large field fluctuations. This paper also provides observations of the effect of these fluctuations on NMR measurements before and after installation of the field-frequency lock system.

Theory and development of biplanar active shim coils for a permanent NMR analyzer.

The general expression for magnetic induction in the z axis direction is derived from magnetic scalar potential, and magnetic induction for biplanar shimming coils (BSCs) is also derived from magnetic vector potentials and Green functions, which simultaneously include Sin and Cos harmonic fields. The relationship between these expressions is discussed, and we show they are partially consistent. Magnetic induction generated Sin and Cos stream functions, which are presented and discussed, and we conclude that the type of stream function determines the type of harmonic field, and that BSCs can not only generate specific harmonic fields directly using Cos stream function, but also generate the rest of the harmonic fields through some specific operations. The detailed design process is presented in the form of a diagram. Subsequently, nine BSCs were calculated using the proposed method and applied to a low field NMR relaxation analyzer. The magnetic field homogeneity after shimming increases significantly, which verifies its practical value.

Fenugreek fibre in bread: Effects on dough development and bread quality

The influences of fenugreek fibre on the hydration and viscoelastic properties of bread dough, as well as the quality of fortified bread were studied using low-field NMR relaxation, farinograph, and texture analyser. Results from farinograph revealed that the incorporation of fenugreek fibre delayed the dough development time and increased the dough stable time. Low field NMR relaxation analysis indicated a distinct interaction of water with wheat flour protein and fenugreek fibre during mixing. Using homestyle Bread Maker, the high fenugreek fibre (9 g/100 g flour) bread with various dough water absorptions was prepared. The impacts of water absorption on bread quality in terms of loaf volume and gas cellular distribution were determined; the texture profiles along storage time were investigated as well, which indicated that fenugreek fibre could maintain bread quality during storage through enhancing the water-holding capacity and lowering starch retrogradation (i.e. staling) rate.

Interactions and exchange of CO2 and H2O in coals: an investigation by low-field NMR relaxation.

The mechanisms by which CO2 and water interact in coal remain unclear and these are key questions for understanding ECBM processes and defining the long-term behaviour of injected CO2. In our experiments, we injected helium/CO2 to displace water in eight water-saturated samples. We used low-field NMR relaxation to investigate CO2 and water interactions in these coals across a variety of time-scales. The injection of helium did not change the T2 spectra of the coals. In contrast, the T2 spectra peaks of micro-capillary water gradually decreased and those of macro-capillary and bulk water increased with time after the injection of CO2. We assume that the CO2 diffuses through and/or dissolves into the capillary water to access the coal matrix interior, which promotes desorption of water molecules from the surfaces of coal micropores and mesopores. The replaced water mass is mainly related to the Langmuir adsorption volume of CO2 and increases as the CO2 adsorption capacity increases. Other factors, such as mineral composition, temperature and pressure, also influence the effective exchange between water and CO2. Finally, we built a quantified model to evaluate the efficiency of water replacement by CO2 injection with respect to temperature and pressure.

A more accurate estimate of [formula omitted] distribution from direct analysis of NMR measurements

In the past decade, low-field NMR relaxation and diffusion measurements in grossly inhomogeneous fields have been used to characterize pore size distribution of porous media. Estimation of these distributions from the measured magnetization data plays a central role in the inference of insitu petro-physical and fluid properties such as porosity, permeability, and hydrocarbon viscosity.In general, inversion of the relaxation and/or diffusion distribution from NMR data is a non-unique and ill-conditioned problem. It is often solved in the literature by finding the smoothest relaxation distribution that fits the measured data by use of regularization.In this paper, estimation of these distributions is further constrained by linear functionals of the measurement that can be directly estimated from the measured data. These linear functionals include Mellin, Fourier–Mellin, and exponential Haar transforms that provide moments, porosity, and tapered areas of the distribution, respectively.The addition of these linear constraints provides more accurate estimates of the distribution in terms of a reduction in bias and variance in the estimates. The resulting distribution is also more stable in that it is less sensitive to regularization. Benchmarking of this algorithm on simulated data sets shows a reduction of artefacts often seen in the distributions and, in some cases, there is an increase of resolution in the features of the T2 distribution. This algorithm can be applied to data obtained from a variety of pulse sequences including CPMG, inversion and saturation recovery and diffusion editing, as well as pulse sequences often deployed down-hole.

Estimation of petrophysical and fluid properties using integral transforms in nuclear magnetic resonance

In the past decade, low-field NMR relaxation and diffusion measurements in grossly inhomogeneous fields have been used to characterize properties of porous media, e.g., porosity and permeability. Pulse sequences such as CPMG, inversion and saturation recovery as well as diffusion editing have been used to estimate distribution functions of relaxation times and diffusion. Linear functionals of these distribution functions have been used to predict petro-physical and fluid properties like permeability, viscosity, fluid typing, etc. This paper describes an analysis method using integral transforms to directly compute linear functionals of the distributions of relaxation times and diffusion without first computing the distributions from the measured magnetization data. Different linear functionals of the distribution function can be obtained by choosing appropriate kernels in the integral transforms. There are two significant advantages of this approach over the traditional algorithm involving inversion of the distribution function from the measured data. First, it is a direct linear transform of the data. Thus, in contrast to the traditional analysis which involves inversion of an ill-conditioned, non-linear problem, the estimates from this new method are more accurate. Second, the uncertainty in the linear functional can be obtained in a straight-forward manner as a function of the signal-to-noise ratio (SNR) in the measured data. We demonstrate the performance of this method on simulated data.