journal article·2019-04-30Open access

Time Domain NMR in Polymer Science: From the Laboratory to the Industry

Denise Besghini, Michele Mauri, Roberto Simonutti

Applied Sciences· Volume 9· Issue 9

Abstract

Highly controlled polymers and nanostructures are increasingly translated from the lab to the industry. Together with the industrialization of complex systems from renewable sources, a paradigm change in the processing of plastics and rubbers is underway, requiring a new generation of analytical tools. Here, we present the recent developments in time domain NMR (TD-NMR), starting with an introduction of the methods. Several examples illustrate the new take on traditional issues like the measurement of crosslink density in vulcanized rubber or the monitoring of crystallization kinetics, as well as the unique information that can be extracted from multiphase, nanophase and composite materials. Generally, TD-NMR is capable of determining structural parameters that are in agreement with other techniques and with the final macroscopic properties of industrial interest, as well as reveal details on the local homogeneity that are difficult to obtain otherwise. Considering its moderate technical and space requirements of performing, TD-NMR is a good candidate for assisting product and process development in several applications throughout the rubber, plastics, composites and adhesives industry.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: NMR spectroscopy and applications · Advanced NMR Techniques and Applications · Advanced MRI Techniques and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Università degli Studi di Milano-Bicocca, Milan, Department of Materials Science, Via R. Cozzi, 55, 20125 Milan, Italy

Trelleborg Coated Systems Italy S.p.A., SP140, 26855 Lodi Vecchio (LO), Italy

References (100+)

Show source-provided references
1. Bicerano, J. (2002). Prediction of Polymers, CRC Press. [3rd ed.]. Revised and Expanded.10.1201/9780203910115 ↗
2. Applications and societal benefits of plastics10.1098/rstb.2008.0304 ↗
3. Schmidt-Rohr, K., and Spiess, H.W. (2012). Multidimensional Solid-State NMR and Polymers, Elsevier.
4. Recent advances in the NMR of solid polymers10.1002/pol.1981.230160105 ↗
5. Nuclear Magnetic-Resonance of Solid Polymers
6. The NMR MOUSE, a Mobile Universal Surface Explorer10.1006/jmra.1996.0185 ↗
7. Goldman, M. (1988). Quantum Description of High-Resolution NMR in Liquids, Oxford University Press.
8. New applications and perspectives of fast field cycling NMR relaxometry10.1002/mrc.4220 ↗
9. Field-Cycling Relaxometry as a Molecular Rheology Technique: Common Analysis of NMR, Shear Modulus and Dielectric Loss Data of Polymers vs Dendrimers10.1021/acs.macromol.5b01805 ↗
10. The influence of polymer molecular-weight distributions on pulsed field gradient nuclear magnetic resonance self-diffusion experiments10.1007/s003960050532 ↗
11. Direct correlation of diffusion and pore size distributions with low field NMR10.1016/j.jmr.2016.06.013 ↗
12. Use of low-field NMR for the characterization of gels and biological tissues10.5599/admet.6.1.430 ↗
14. Modified spin-echo method for measuring nuclear relaxation times10.1063/1.1716296 ↗
15. Categories of Coherence Pathways for the CPMG Sequence10.1006/jmre.2002.2577 ↗
16. Basic principles of static proton low-resolution spin diffusion NMR in nanophase-separated materials with mobility contrast10.1016/j.ssnmr.2015.09.001 ↗
17. Spin-Lattice Relaxation Measurements in Slowly Relaxing Complex Spectra10.1063/1.1676626 ↗
18. Effects of diffusion on free precession in nuclear magnetic resonance experiments10.1103/PhysRev.94.630 ↗
19. Spin-Lattice Relaxation in the Rotating Frame: Weak-Collision Case10.1103/PhysRev.148.332 ↗
20. Inorganic-organic hybrids based on poly (ε-Caprolactone) and silica oxide and characterization by relaxometry applying low-field NMR10.1590/S1516-14392012005000121 ↗
21. Saalwächter, K. (2017). Multiple-Quantum NMR Studies of Anisotropic Polymer Chain Dynamics. Modern Magnetic Resonance, Springer International Publishing AG.10.1007/978-3-319-28275-6_59-2 ↗
22. NMR Studies of Clustering in Solids10.1021/ja00284a001 ↗
23. Proton multiple-quantum NMR for the study of chain dynamics and structural constraints in polymeric soft materials10.1016/j.pnmrs.2007.01.001 ↗
24. Residual dipolar couplings by 1H dipolar-encoded longitudinal magnetization, double- and triple-quantum nuclear magnetic resonance in cross-linked elastomers10.1063/1.479291 ↗
25. Multispin moments edited by multiple-quantum NMR: Application to elastomers10.1016/j.jmr.2004.10.001 ↗
26. A Robust Proton NMR Method to Investigate Hard/Soft Ratios, Crystallinity, and Component Mobility in Polymers10.1002/macp.200600169 ↗
27. 1H multiple-quantum nuclear magnetic resonance investigations of molecular order distributions in poly(dimethylsiloxane) networks: Evidence for a linear mixing law in bimodal systems10.1063/1.1589000 ↗
28. Domain sizes in heterogeneous polymers by spin diffusion using single-quantum and double-quantum dipolar filters10.1016/S0926-2040(03)00020-1 ↗
29. Spin diffusion in resolved solid-state NMR spectra10.1103/PhysRevB.32.5608 ↗
30. Nuclear Spin Diffusion between Polyurethane Microphases10.1021/ma60066a031 ↗
31. Spin-Spin Relaxation in LaF310.1103/PhysRev.144.321 ↗
32. A Modified Goldman-Shen NMR Pulse Sequence10.1016/0009-2614(89)80079-X ↗
33. Dipolar filtered magic-sandwich-echoes as a tool for probing molecular motions using time domain NMR10.1016/j.jmr.2017.10.008 ↗
34. Analysis of solid technical polymers by compact NMR10.1016/j.trac.2016.04.003 ↗
35. Schäler, K. (2013). Low-Field Nmr Studies of Structure and Dynamics in Semicrystalline Polymers. [Ph.D. Thesis, Institut für Physik der Naturwissenschaftlichen Fakultät II der Martin-Luther-Universität Halle-Wittenberg].
36. Spin-diffusion NMR at low field for the study of multiphase solids10.1016/j.ssnmr.2008.07.001 ↗
37. Rapid and simple determination of T1 relaxation times in time-domain NMR by Continuous Wave Free Precession sequence10.1016/j.jmr.2016.06.019 ↗
38. Simultaneous measurements of T1 and T2 during fast polymerization reaction using continuous wave-free precession NMR method10.1002/mrc.3834 ↗
39. On the numerical inversion of the Laplace transform for nuclear magnetic resonance relaxometry10.1088/0266-5611/17/1/307 ↗
40. On the numerical inversion of the Laplace transform and similar Fredholm integral equations of the first kind10.1088/0305-4470/11/9/007 ↗
41. Heterogeneity of nanofilled EPDM elastomers investigated by inverse laplace transform 1H NMR relaxometry and rheometry10.1002/macp.201000086 ↗
42. The Theory of Tikhonov Regularization for Fredholm Equations of the First Kind
43. Significance of materials science for the future development of societies10.1016/j.jmatprotec.2005.04.003 ↗
44. Heterogeneity, segmental and hydrogen bond dynamics, and aging of supramolecular self-healing rubber10.1021/ma400019m ↗
45. Moisture-mediated self-healing kinetics and molecular dynamics in modified polyurethane urea polymers10.1016/j.polymer.2018.07.059 ↗
46. Characterization of network structure and chain dynamics of elastomeric ionomers by means of 1H Low-Field NMR10.1021/ma501208g ↗
47. Effect of Rubber Polarity on Cluster Formation in Rubbers Cross-Linked with Diels-Alder Chemistry10.1021/acs.macromol.7b01541 ↗
48. Study of Aliphatic Polyurethanes by the Low-Field 1H NMR Relaxometry Method with the Inversion of the Integral Transformation
49. Size-Controlled Nanomicelles of Poly(lactic acid)–Poly(ethylene glycol) Copolymers with a Multiblock Configuration10.3390/polym7061177 ↗
50. Thermoresponsive low-power light upconverting polymer nanoparticles10.1039/C6MH00290K ↗
51. Core@shell Poly(n-butylacrylate)@polystyrene Nanoparticles: Baroplastic Force-Responsiveness in Presence of Strong Phase Separation10.1002/marc.201500625 ↗
52. The Effect of para-divinyl benzene on styrenic emulsion-templated porous polymers: A chemical trojan horse10.1007/s10853-016-0607-z ↗
53. Structure of polyvinyl alcohol cryo-hydrogels as studied by proton low-field NMR spectroscopy10.1021/ma802172g ↗
54. Time domain NMR evaluation of poly(vinyl alcohol) xerogels10.1590/0104-1428.2093 ↗
55. Solid-State Sensitized Upconversion in Polyacrylate Elastomers10.1021/acs.jpcc.6b00223 ↗
56. Chain Entanglements in Polyethylene Melts. Why Is It Studied Again?10.1021/ma302394j ↗
57. Reptation of a polymer chain in the presence of fixed obstacles10.1063/1.1675789 ↗
58. Dynamics of Concentrated Polymer Systems Part 3
59. Pseudo-solid echoes of proton and deuteron NMR in polyethvlene melts10.1007/BF01381764 ↗
60. Time-domain NMR observation of entangled polymer dynamics: Analytical theory of signal functions10.1021/ma102571u ↗
61. Time-domain NMR observation of entangled polymer dynamics: Universal behavior of flexible homopolymers and applicability of the tube model10.1021/ma1025708 ↗
62. From Simple Liquid to a Polymer Melt. Glassy and Polymer Dynamics Studied by Fast Field Cycling NMR Relaxometry: Low and High Molecular Weight Limit10.1021/ma702771s ↗
63. Polymer dynamics of polybutadiene in nanoscopic confinement as revealed by field cycling 1H NMR10.1021/ma2002504 ↗
64. Glassy, rouse, and entanglement dynamics as revealed by field cycling 1H NMR relaxometry10.1021/ma202371p ↗
65. Mordvinkin, A., and Saalwächter, K. (2017). Microscopic observation of the segmental orientation autocorrelation function for entangled and constrained polymer chains. J. Chem. Phys., 146.10.1063/1.4977041 ↗
66. Contribution of Entanglements to Polymer Network Elasticity10.1021/acs.macromol.6b02784 ↗
67. Probing small network differences in sulfur-cured rubber compounds by combining nuclear magnetic resonance and swelling methods10.1002/app.42700 ↗
68. Gotlib, Y.Y., Lifshits, M.I., Shevelev, V.A., Lishanskii, I.S., and Balanina, I.V. (1976). The influence of the chemical crosslinking network on the spin-spin relaxation of crosslinked and swelling polymer systems. Polym. Sci. U.S.S.R., 18.10.1016/0032-3950(76)90192-1 ↗
69. Network Structure in Acrylate Systems: Effect of Junction Topology on Cross-Link Density and Macroscopic Gel Properties10.1021/acs.macromol.6b01070 ↗
70. Chain mobility in crosslinked EPDM rubbers. Comparison of 1H NMR T2 relaxometry and double-quantum 1H NMR10.1021/bk-2011-1077.ch013 ↗
71. Chain Dynamics and Strain-Induced Crystallization of Pre- and Postvulcanized Natural Rubber Latex Using Proton Multiple Quantum NMR and Uniaxial Deformation by in Situ Synchrotron X-ray Diffraction10.1021/ma3006894 ↗
72. Mechanism for Peroxide Cross-Linking of EPDM Rubber from MAS 13C NMR Spectroscopy10.1021/ma9016482 ↗
73. New Insights into Structural Development in Natural Rubber during Uniaxial Deformation by In Situ Synchrotron X-ray Diffraction10.1021/ma0205921 ↗
74. Orientation-dependent proton double-quantum NMR build-up function for soft materials with anisotropic mobility10.1016/j.ssnmr.2017.01.006 ↗
75. Epoxy resin curing reaction studied by proton multiple-quantum NMR10.1002/polb.23767 ↗
76. Development of low field NMR technique for analyzing segmental mobility of crosslinked polymers10.1002/polb.24583 ↗
77. Rubber-filler interactions and network structure in relation to stress-strain behavior of vulcanized, carbon black filled EPDM10.1021/ma2007255 ↗
78. Low-field NMR investigations of nanocomposites: Polymer dynamics and network effects10.1021/ma102486x ↗
79. The filler-rubber interface in styrene butadiene nanocomposites with anisotropic silica particles: Morphology and dynamic properties10.1039/C5SM00536A ↗
80. Borsacchi, S., Sudhakaran, U.P., Calucci, L., Martini, F., Carignani, E., Messori, M., and Geppi, M. (2018). Rubber-filler interactions in polyisoprene filled with in situ generated silica: A solid state NMR study. Polymers, 10.10.3390/polym10080822 ↗
81. Novel Experimental Approach to Evaluate Filler-Elastomer Interactions10.1021/ma901999j ↗
82. Mauri, M., Floudas, G., and Simonutti, R. (2018). Local order and dynamics of nanoconstrained ethylene-butylene chain segments in SEBS. Polymers, 10.10.3390/polym10060655 ↗
83. Low-field NMR studies of polymer crystallization kinetics: Changes in the melt dynamics10.1016/j.polymer.2006.03.117 ↗
84. NMR study of interphase structure in layered polymer morphologies with mobility contrast: Disorder and confinement effects vs. dynamic heterogeneities10.1007/s00396-014-3218-8 ↗
85. Complex Morphology of the Intermediate Phase in Block Copolymers and Semicrystalline Polymers as Revealed by 1H NMR Spin Diffusion Experiments10.1021/acs.macromol.7b00703 ↗
86. Keratin based bioplastic film from chicken feathers and its characterization10.1016/j.ijbiomac.2018.01.037 ↗
87. Thermo-mechanical and hydrophilic properties of polysaccharide/gluten-based bioplastics10.1016/j.carbpol.2014.05.055 ↗
88. Liebeck, B.M., Hidalgo, N., Roth, G., Popescu, C., and Böker, A. (2017). Synthesis and Characterization of Methyl Cellulose/Keratin Hydrolysate Composite Membranes. Polymers, 9.10.3390/polym9030091 ↗
89. Industrial potential of polyhydroxyalkanoate bioplastic: A brief review
90. Properties and applications of compostable starch-based plastic material10.1016/S0141-3910(97)00168-7 ↗
91. Development of highly-transparent protein/starch-based bioplastics10.1016/j.biortech.2009.10.025 ↗
92. A Review on Starch Based Nanocomposites for Bioplastic Materials
93. Vismara, E., Bongio, C., Coletti, A., Edelman, R., Serafini, A., Mauri, M., Simonutti, R., Bertini, S., Urso, E., and Assaraf, Y.G. (2017). Albumin and hyaluronic acid-coated superparamagnetic iron oxide nanoparticles loaded with paclitaxel for biomedical applications. Molecules, 22.10.3390/molecules22071030 ↗
94. Solid-State NMR Investigation of Paramagnetic Nylon-6 Clay Nanocomposites. 1. Crystallinity, Morphology, and the Direct Influence of Fe3+ on Nuclear Spins10.1021/cm0110775 ↗
95. Proton NMR relaxometry as probe of gelatinization, plasticization and montmorillonite-loading effects on starch-based materials10.1016/j.carbpol.2017.11.021 ↗
96. NMR relaxometry evaluation of nanostructured starch-PLA blends10.1016/j.polymertesting.2015.06.011 ↗
97. Wang, P., Sheng, F., Tang, S.W., ud-Din, Z., Chen, L., Nawaz, A., Hu, C., and Xiong, H. (2018). Synthesis and Characterization of Corn Starch Crosslinked with Oxidized Sucrose. Starch Stärke, 1800152.10.1002/star.201800152 ↗
98. Bioplastics from vegetable waste: Via an eco-friendly water-based process10.1039/C7GC03368K ↗
99. An NMR relaxation and spin diffusion study of cellulose structure during water adsorption10.1134/S0006350917020087 ↗
100. Correlation between traditional techniques and TD-NMR to determine the morphology of PHB/PCL blends10.1016/j.polymertesting.2016.11.036 ↗