Hyphenated low-field NMR techniques are promising characterization methods for online process analytics and comprehensive offline studies of soft materials. By combining different analytical methods with low-field NMR, information on chemical and physical properties can be correlated with molecular dynamics and complementary chemical information. In this review, we present three hyphenated low-field NMR techniques: a combination of near-infrared spectroscopy and time-domain NMR (TD-NMR) relaxometry, online (1) H-NMR spectroscopy measured directly after size exclusion chromatographic (SEC, also known as GPC) separation and a combination of rheometry and TD-NMR relaxometry for highly viscous materials. Case studies are reviewed that underline the possibilities and challenges of the different hyphenated low-field NMR methods. Copyright © 2015 John Wiley & Sons, Ltd.

Semi crystalline polymers play an enormously important role in materials science, engineering, and nature. Two thirds of all synthetic polymers have the ability to crystallize which allows for the extensive use of these materials in a variety of applications as molded parts, films, or fibers. Here, we present a study on the applicability of benchtop 1 H NMR relaxometry to obtain information on the bulk crystal linity and crystallization kinetics of the most relevant synthetic semi crystalline polymers. In the first part, we investigated the temperature dependent relaxation behavior and identified T ¼ T g þ 100 K as the minimum relative temperature difference with respect to T g for which the mobility contrast between crystalline and amorphous protons is sufficient for an unambiguous determination of polymer crystal linity. The obtained bulk crystallinities from 1 H NMR were compared to results from DSC and XRD, and all three methods showed relatively good agreement for all polymers. In the second part, we focused on the determination of the crystallization kinetics, i.e., monitoring of isothermal crystallization, which required a robust design of the pulse sequence, precise temperature calibration, and careful data analysis. We found the combination of a magic sandwich echo (MSE) with a short acquisition time followed by a Carr Purcell Meiboom Gill (CPMG) echo train with short pulse timings to be the most suitable for monitoring crystallization. This study demonstrates the application of benchtop 1 H NMR relaxometry to investigate the bulk crystallinity and crystallization kinetics of polymers, which can lead to its optimal use as an in situ technique in research, quality control, and processing labs.

Rheological set‐ups with in situ analytical sensors, combine information on the flow and deformation behavior of soft matter, with simultaneous insights into structural and dynamic features. Furthermore, they permit the study of soft matter under well‐defined flow conditions. Herein are presented hyphenations of rheology and nuclear magnetic resonance (NMR), small angle X‐ray scattering (SAXS), and optical microscopy. They are employed to unravel relationships between the molecular dynamics, morphology, and rheology of crystallizing polymers. The results confirm a physical gelation process during polymer crystallization, mediated by the interaction of growing superstructures at volume fractions of 10–15%. The buildup of row‐nucleated structures during flow‐induced crystallization is found to reduce the time of gelation as detected by the rheological response. These investigations help to clarify the crystallization mechanism, structure–property relationships, and the hardening behavior of crystallizing polymers.

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Low‐field NMR relaxometry is sensitive to molecular mobility within well‐defined time windows and can thus be applied to study interactions between polymers and inorganic filler particles in composite materials. Volume fraction and dispersion of the filler influence the polymer chain dynamics, which also modify the macroscopic properties of the polymer composites. As model systems, TiO2‐filled poly(n‐alkyl methacrylates) with different side‐chain lengths and filler contents are prepared by melt mixing. Several 1H NMR relaxation parameters, which are sensitive and selective toward polymer–filler interactions, are investigated at a Larmor frequency of 20 MHz as a function of temperature. Both physical and empirical models are used to analyze the NMR data, and the results are compared with the aim of an unambiguous detection of polymer–filler interactions.