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Electrospun fibers of amorphous or low-crystallinity polymers typically exhibit a low molecular orientation that can hamper their properties and application. A key stage of the electrospinning process that could be harnessed to mitigate the loss of orientation is jet rigidification, which relates closely to the solvent evaporation rate. Here, we establish quantitative Raman methods to assess the molecular orientation and crystallinity of weakly crystalline poly(2,6-dimethyl-1,4-phenylene oxide) fibers with varying diameters. Our findings demonstrate that solvent volatility can be leveraged to modulate the orientation and crystallinity through its impact on the effective glass transition temperature ( T g,eff ) of the polymer jet during the electrospinning process. Specifically, a highly volatile solvent yields a higher and more sustained orientation (median ⟨ P 2 ⟩ of 0.53 for diameters < 1.0 µm) because its fast evaporation rapidly increases T g,eff above room temperature. This vitrification early along the jet path promotes the formation of an oriented amorphous phase and a moderate fraction of strain-induced crystals. Our data reveals that a high T g is a crucial parameter for reaching high orientation in amorphous or low-crystallinity polymer systems., Competing Interests: Declaration of Conflicting InterestsThe authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

*These authors contributed equally.Electrospun fibers often exhibit enhanced properties at reduced diameters, a characteristic now widely attributed to a high molecular orientation of the polymer chains along the fiber axis. A parameter that can affect the molecular organization is the type of collector onto which fibers are electrospun. In this work, we use polarized confocal Raman spectromicroscopy to determine the incidence of the three most common types of collectors on the molecular orientation and structure in individual fibers of a broad range of diameters. Poly(ethylene terephthalate) is used as a model system for fibers of weakly crystalline polymers. A clear correlation emerges between the choice of collector, the induced molecular orientation, the fraction of trans conformers, and the degree of crystallinity within fibers. Quantitative structural information gathered by Raman contributes to a general description of the mechanism of action of the collectors based on the additional strain they exert on the forming fibers.

Polarized Raman spectroscopy is widely used to quantify the level of molecular orientation of various types of materials. By using a simplified procedure we call the depol (depolarization) constant (DC) method, since it assumes that the depolarization ratio is a constant. However, our ability to quantify orientation by using the DC method is often limited by the need for a completely isotropic sample showing the same chemical and phase composition as the oriented sample of interest to obtain information on the depolarization ratio. In this paper, we propose a new method for orientation quantification, the most probable distribution (MPD) method, based on the hypothesis that the population distribution is the most probable one. In contrast to the conventional DC procedure, this new method does not require knowledge of the depolarization ratio and eliminates the assumption that it does not evolve on orientation. Simulations show the wide applicability of the MPD method for large sections of the 〈P2〉 〈P4〉 diagram, especially for coordinates that are most likely to be observed in experimental conditions. They also highlight the significant inaccuracies produced by the conventional DC method due to depolarization ratio errors.

Polarization modulation infrared linear dichroism (PM-IRLD) is often used for measurements of molecular orientation with high sensitivity and good time resolution. However, PM-IRLD is unable to provide the structural absorbance spectrum because it does not measure separately the parallel and perpendicular spectra. Here we propose a new method, named polarization modulation infrared structural absorbance spectroscopy (PM-IRSAS), to overcome this limitation of PM-IRLD. PM-IRSAS measures the dichroic difference and structural absorbance spectra simultaneously and, therefore, allows quantitative analysis of molecular orientation and conformation with 200 ms time resolution. The PM-IRSAS method was first validated through comparison with conventional polarized FT-IR spectroscopy using drawn polymer films. Second, it was demonstrated that the PM-IRSAS method can provide a quantitative analysis of dynamic orientation and conformation changes in PET films during deformation and crystallization processes.

A planar array infrared (PA-IR) spectrograph offers several advantages over other infrared approaches, including high acquisition rate and sensitivity. However, it suffers from some important drawbacks, such as a limited spectral range and a significant curvature of the recorded spectral images, which still need to be addressed. In this article, we present new developments in PA-IR spectroscopy that overcome these drawbacks. First, a data processing method for the correction of the curvature observed in the spectral images has been developed and refined. In addition, a dual-beam instrument that allows the simultaneous recording of two independent spectral images has been developed. These two improvements have been combined to demonstrate the real-time background correction capability of PA-IR instruments. Finally, the accessible spectral range of the PA-IR spectrograph has been extended to cover simultaneously the methylene stretching (3200-2800 cm(-1)) and the finger-print (2000-1000 cm(-1)) spectral regions.

Infrared rheo-optics combines dynamic mechanical analysis with infrared spectroscopy to provide molecular level information about the segmental reorientation and the changes in local environment associated with the dynamic deformation of polymers. Up to now, the application of this technique has been limited by the amount of time necessary to perform the experiments. In this article, we demonstrate that the use of a planar array infrared (PA-IR) spectrograph can accelerate the acquisition time by as much as two orders of magnitude while maintaining a signal-to-noise ratio (SNR) similar to that obtained using step-scan Fourier transform infrared (FT-IR) spectrometry, and by more than three orders of magnitude at the expense of a reduced SNR. The advantages and drawbacks of this new technique are discussed.

A no-moving-part planar array infrared spectrograph (PA-IR) equipped with a 256 x 256 mercury cadmium telluride (MCT) focal plane array has been designed and constructed. The performance of the instrument, whose frequency range extends from 2000-975 cm(-1), has been assessed in terms of resolution, bandwidth, and signal-to-noise ratio. The PA-IR spectrograph is able to record spectra with an 8.7 ms time resolution and has peak-to-peak noise levels as low as 2.4 x 10(-4) A.U. As a demonstration of the potential of PA-IR, the dynamics of reorientation of a liquid crystalline sample exposed to a single electric field pulse has been studied. It was shown that PA-IR can be used for the simultaneous acquisition of two orthogonally polarized spectra. The advantages and limitations of PA-IR, step-scan Fourier transform infrared (FT-IR), and ultrarapid-scanning FT-IR for real-time studies of reversible and irreversible phenomena are thoroughly discussed.