NMR relaxometry of oil paint binders.

Mobile nuclear magnetic resonance (NMR) is a flexible technique for nondestructive characterization of water in plants, the physical properties of polymers, moisture in porous walls, or the binder in paintings by relaxation measurements. NMR relaxation data report material properties and therefore can also help to characterize the state of tangible cultural heritage. In this work, we discuss the relaxation behavior in two series of naturally aged paint mock-up samples. First, paints with different pigment concentrations were prepared and investigated in terms of the longitudinal and transverse relaxation-time distributions. We document the evolution of both relaxation-time distributions during the initial drying stage and demonstrate the heightened importance of transverse over longitudinal relaxation measurements. Second, we observe nonlinear dependences of the relaxation times on the pigment concentration in a typical oil binder. Third, in a study of naturally aged paint samples prepared in the years between 1914 and 1951 and subsequently aged under controlled conditions, we explore the possibility of determining the age of paintings using partial least square regression (PLS) by fitting T1 -T2 data with the sample age. Our results suggest some correlation, albeit with significant scatter. Estimating the age of a painting stored under unknown conditions from NMR relaxation data is therefore not feasible, as the cumulative effects of light irradiation, humidity, and biological degradation further obfuscate the chemical and physical impact of aging on the relaxation times in addition to the impact of pigment concentration.

Visualizing the detection area of a unilateral NMR sensor using deconvolution and back-projection.

Understanding the detection volume of a unilateral NMR sensor is crucial to interpret acquired data appropriately. Whereas this is easily done in the sensor's axial dimension by running a depth profile on a well-defined sample, the lateral dimension is commonly characterized with very small samples, where each position along a regular grid is scanned individually, typically resulting in measurement times of several days and a resolution that is limited to the dimensions of the sample. Here we apply two mathematical procedures known from image processing that employ samples larger than the pixel size to characterize the lateral detection area. One procedure uses deconvolution algorithms to account for blurring effects caused by a larger sample while the other utilizes back-projection of radial field profiles. Both approaches are demonstrated with a Profile NMR-MOUSE® (PM5). They yield field maps in good agreement with those acquired with pixel-size test samples but save about one order of magnitude in scanning time.

Cultural Heritage Studies with Mobile NMR.

Nuclear magnetic resonance (NMR) provides in situ information about selected isotope densities in samples and objects, while also providing contrast through rotational and translational molecular dynamics. These parameters are probed not only in NMR spectroscopy and imaging but also in nondestructive materials testing by mobile stray-field NMR, the unique properties of which are valuable in cultural heritage studies. We present recent progress in the analysis of cultural heritage with mobile 1 H NMR stray-field sensors, for which the detection zone is outside of the NMR magnet. Prominent applications include the analysis of stratigraphies in paintings and frescoes, and the assessment of material states changing under the impact of aging, conservation, and restoration.

A size-adjustable radiofrequency coil for investigating plants in a Halbach magnet.

A radio-frequency coil with adjustable distance has been developed and tested for in-situ examination of growing plants. The Helmholtz-based coil design reduces laborious tuning and matching efforts encountered with solenoids wound around a growing stem or branch. Relaxation experiments were performed on tomato plants and winter wheat under controlled light irradiation. Changes in signal amplitude and in relaxation times T2 were recorded over day and night cycles. Peaks in distributions of relaxation times were attributed to different tissue components of two different plants.

Shimming Halbach magnets utilizing genetic algorithms to profit from material imperfections.

In recent years, permanent magnet-based NMR spectrometers have resurfaced as low-cost portable alternatives to superconducting instruments. While the development of these devices as well as clever shimming methods have yielded impressive advancements, scaling the size of these magnets to miniature lengths remains a problem to be addressed. Here we present the results of a study of a discrete shimming scheme for NMR Mandhalas constructed from a set of individual magnet blocks. While our calculations predict a modest reduction in field deviation by a factor of 9.3 in the case of the shimmed ideal Mandhala, a factor of 28 is obtained in the case of the shimmed imperfect Mandhala. This indicates that imperfections of magnet blocks can lead to improved field homogeneity. We also present a new algorithm to improve the homogeneity of a permanent magnet assembly. Strategies for future magnet construction can improve the agreement between simulation and practical implementation by using data from real magnets in these assemblies as the input to such an algorithm to optimize the homogeneity of a given design.

Miniaturized multi-coil arrays for functional planar imaging with a single-sided NMR sensor.

Nowadays most low-field NMR sensors, such as the single-sided Profile NMR-MOUSE®, still suffer from poor sensitivity, either resulting from low magnetic field strengths and correspondingly low NMR frequencies, or lack of sensitivity. Generally, micro-coils can improve sensitivity, but due to their small size, and thus small inductance, they are mainly used for high-field NMR. Their main application field is parallel imaging, where those coils are typically assembled to receive-only coil-arrays and increase the field-of-view. Prominent signal combination techniques such as GRAPPA and SENSE are used to combine the spatially independent NMR signals to images in order to increase acquisition speed. A decisive disadvantage of today's single-sided NMR probes is the limited accessibility for NMR imaging. Although it is possible to use flat gradient coils on top of the NMR-MOUSE® to apply imaging techniques, such images can only be recorded with very long acquisition times, excluding the NMR-MOUSE® for lateral imaging of time-dependent processes. In this study sensitivity improved micro-structured RF coils, optimized for low frequencies, and correspondingly arrays of these coils, were employed to improve sensitivity and gave access to lateral spatial resolution within the sensitive plane at several observation points at the same time. Recently developed three- and four-coil arrays were combined with a Profile NMR-MOUSE® and characterized in terms of coil coupling, noise correlation and signal combination. The three-coil array was used for lateral imaging of moisture transport in travertine rock samples and to study the one-dimensional drying of paint.