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Transient Confinement of the Quaternary Tetramethylammonium Tetrafluoroborate Salt in Nylon 6,6 Fibres: Structural Developments for High Performance Properties.

ABSTRACT: A temporary confinement of the quaternary tetramethylammonium tetrafluoroborate (TMA BF₄) salt among polyamide molecules has been used for the preparation of aliphatic polyamide nylon 6,6 fibres with high-modulus and high-strength properties. In this method, the suppression or the weakening of the hydrogen bonds between the nylon 6,6 segments has been applied during the conventional low-speed melt spinning process. Thereafter, after the complete hot-drawing stage, the quaternary ammonium salt is fully extracted from the drawn 3 wt.% salt-confined fibres and the nascent fibres are, subsequently, thermally stabilized. The structural developments that are acquired in the confined-nylon 6,6 fibres are ascribed to the developments of the overall fibres' properties due to the confinement process. Surprisingly, unlike the neat nylon 6,6 fibres, the X-ray diffraction (XRD) patterns of the as-spun salt-confined fibres have shown diminishing of the (110)/(010) diffraction plane that obtained pseudohexagonal-like β' structural phase. Moreover, the β' pseudohexagonal-like to α triclinic phase transitions took-place due to the hot-drawing stage (draw-induced phase transitions). Interestingly, the hot-drawing of the as-spun salt-confined nylon 6,6 fibres achieved the same maximum draw ratio of 5.5 at all of the drawing temperatures of 120, 140 and 160 °C. The developments that happened produced the improved values of 43.32 cN/dtex for the tensile-modulus and 6.99 cN/dtex for the tensile-strength of the reverted fibres. The influences of the TMA BF₄ salt on the structural developments of the crystal orientations, on the morphological structures and on the improvements of the tensile properties of the nylon 6,6 fibres have been intensively studied.

SUBMITTER: Dawelbeit A

PROVIDER: S-EPMC8198042 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:A reversible confinement of ionic liquid (IL) among the amide segments has been carried out for the preparation of high-modulus and high-strength aliphatic semicrystalline nylon 6 fibers. In this research work, the suppression or the weakening of the hydrogen bonds during the conventional low-speed melt spinning process is followed by a hot-drawing stage and a subsequent IL extraction of the IL out of the 2% wt IL-confined fibers and an immediate thermal stabilization process for the improvement of the properties of the pristine nylon 6 fibers. The resulted crystal structural developments of the IL-confined fibers are attributed to ultimate molecular orientations, which have contributed to the developments of the overall fiber properties. Here, the influences of the IL on the γ and the α crystal phases, the γ-α transition, the morphological properties, and the tensile properties are investigated. The FTIR reported, experimentally, additional peaks at 1237 cm-1 for the γ crystal phase and at 1417 and 1476 cm-1 for the α crystal phase, in conformity with the theoretical computations. The XRD demonstrated that the conventional low-speed melt spinning can successfully be used to prepare as-spun IL-confined fibers having highly improved properties. The so prepared as-spun IL-confined fibers are found to have a γ phase structure that has a small crystal size and high crystal perfections. Fortunately, the γ-to-α crystal phase transition for the IL-confined nylon 6 fibers can be acquired during the hot-drawing stage (stress-induced phase transformation). Furthermore, the IL extraction process followed by a thermal stabilization process, interestingly, has led to significant increases in both of the tensile strengths and the tensile moduli of the reverted nylon 6 fibers. The values that are found are 8.46 cN/dtex for the tensile strength and 39.09 cN/dtex for the tensile modulus. The structure-property relationships between the IL-confined and the reverted nylon 6 fibers have also been discussed.

Project description:Tendon and ligament injuries are triggered by mechanical loading, but the specific mechanisms are not yet clearly identified. It is well established however, that the inflection and transition points in tendon stress-strain curves represent thresholds that may signal the onset of irreversible fibrillar sliding. This phenomenon often results in a progressive macroscopic failure of these tissues. With the aim to simulate and replace tendons, electrospinning has been demonstrated to be a suitable technology to produce nanofibers similar to the collagen fibrils in a mat form. These nanofibrous mats can be easily assembled in higher hierarchical levels to reproduce the whole tissue structure. Despite the fact that several groups have developed electrospun tendon-inspired structures, an investigation of the inflection and transition point mechanics is missing. Comparing their behavior with that of the natural counterpart is important to adequately replicate their behavior at physiological strain levels. To fill this gap, in this work fascicle-inspired electrospun nylon 6,6 bundles were produced with different collector peripheral speeds (i.e., 19.7 m s-1; 13.7 m s-1; 7.9 m s-1), obtaining different patterns of nanofibers alignment. The scanning electron microcopy revealed a fibril-inspired structure of the nanofibers with an orientation at the higher speed similar to those in tendons and ligaments (T/L). A tensile mechanical characterization was carried out showing an elastic-brittle biomimetic behavior for the higher speed bundles with a progressively more ductile behavior at slower speeds. Moreover, for each sample category the transition and the inflection points were defined to study how these points can shift with the nanofiber arrangement and to compare their values with those of tendons. The results of this study will be of extreme interest for the material scientists working in the field, to model and improve the design of their electrospun structures and scaffolds and enable building a new generation of artificial tendons and ligaments.

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Transient Confinement of the Quaternary Tetramethylammonium Tetrafluoroborate Salt in Nylon 6,6 Fibres: Structural Developments for High Performance Properties.

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