Ultra-wideline 14N solid-state NMR as a method for differentiating polymorphs: glycine as a case study

Nitrogen-14 solid-state NMR (SSNMR) is utilized to differentiate three polymorphic forms and a hydrochloride (HCl) salt of the amino acid glycine. Frequency-swept Wideband, Uniform Rate, Smooth Truncated (WURST) pulses were used in conjunction with Carr-Purcell Meiboom-Gill refocusing, in the form of the WURST-CPMG pulse sequence, for all spectral acquisitions. The ¹⁴N quadrupolar interaction is shown to be very sensitive to variations in the local electric field gradients (EFGs) about the ¹⁴N nucleus; hence, differentiation of the samples is accomplished through determination of the quadrupolar parameters CQ and ηQ, which are obtained from analytical simulations of the ¹⁴N SSNMR powder patterns of stationary samples (i.e., static NMR spectra). Additionally, differentiation of the polymorphs is also possible via the measurement of ¹⁴N effective transverse relaxation time constants, T^eff2(¹⁴N). Plane-wave density functional theory (DFT) calculations, which exploit the periodicity of crystal lattices, are utilized to confirm the experimentally determined quadrupolar parameters as well as to determine the orientation of the ¹⁴N EFG tensors in the molecular frames. Several signal-enhancement techniques are also discussed to help improve the sensitivity of the ¹⁴N SSNMR acquisition method, including the use of selective deuteration, the application of the BRoadband Adiabatic INversion Cross-Polarization (BRAIN-CP) technique, and the use of variable-temperature (VT) experiments. Finally, we examine several cases where ¹⁴N VT experiments employing Carr-Purcell-Meiboom-Gill (CPMG) refocusing are used to approximate the rotational energy barriers for RNH3⁺ groups.

Formation of ultra-fine ferrite in hot rolled strip: potential mechanisms for grain refinement

A novel single-pass hot strip rolling process has been developed in which ultra-fine (<2 μm) ferrite grains form at the surface of hot rolled strip in two low carbon steels with average austenite grain sizes above 200 μm. Two experiments were performed on strip that had been re-heated to 1250°C for 300 s and air-cooled to the rolling temperatures. The first involved hot rolling a sample of 0.09 wt.%C–1.68Mn–0.22Si–0.27Mo steel (steel A) at 800°C, which was just above the Ar3 of this sample, while the second involved hot rolling a sample of 0.11C–1.68Mn–0.22Si steel (steel B) at 675°C, which is just below the Ar3 temperature of the sample. After air cooling, the surface regions of strip of both steel A and B consisted of ultra-fine ferrite grains which had formed within the large austenite grains, while the central regions consisted of a bainitic microstructure. In the case of steel B, a network of allotriomorphic ferrite delineated the prior-austenite grain boundaries throughout the strip cross-section. Based on results from optical microscopy and scanning/transmission electron microscopy, as well as bulk X-ray texture analysis and microtextural analysis using Electron Back-Scattered Diffraction (EBSD), it is shown that the ultra-fine ferrite most likely forms by a process of rapid intragranular nucleation during, or immediately after, deformation. This process of inducing intragranular nucleation of ferrite by deformation is referred to as strain-induced transformation.