Boosting fire safety and mechanical performance of thermoplastic polyurethane by the face-to-face two-dimensional phosphorene/MXene architecture

doi:10.1016/j.jmst.2022.05.003

Abstract

Abstract:

Black phosphorus (BP), as one of the most promising fillers for flame retarding polymer, has been seriously limited in practical application, due to the agglomeration and poor structural stability challenges. Here, the BP was modified by MXene and polydopamine (PDA) via ultrasonication and dopamine modification strategy to improve the structural stability and dispersibility in the matrix. Then, the obtained (BP-MXene@PDA) nanohybrid was employed to promote the mechanical performance, thermal stability, and flame retardancy of thermoplastic polyurethane elastomer (TPU). The resultant TPU composite containing 2 wt.% of BP1-MXene2@PDA showed a 19.2% improvement in the tensile strength and a 13.8% increase in the elongation at break compared to those of the pure TPU. The thermogravimetric analysis suggested that BP-MXene@PDA clearly enhances the thermal stability of TPU composites. Furthermore, the introduction of the BP-MXene@PDA nanohybrids could considerably improve the flame retardancy of TPU composite, i.e., 64.2% and 27.3% decrease in peak heat release rate and total heat release, respectively. The flame-retardant mechanisms of TPU/BP-MXene@PDA in the gas phase and condensed phase were investigated systematically. This work provides a novel strategy to simultaneously enhance the fire safety and mechanical properties of TPU, thus expanding its industrial applications.

Key words: Thermoplastic polyurethane elastomer, Black phosphorus, MXene, Mechanical properties, Flame retardancy

Yong Luo, Yuhui Xie, Wei Geng, Junhan Chu, Hua Wu, Delong Xie, Xinxin Sheng, Yi Mei. Boosting fire safety and mechanical performance of thermoplastic polyurethane by the face-to-face two-dimensional phosphorene/MXene architecture[J]. J. Mater. Sci. Technol., 2022, 129: 27-39.

Figures/Tables 17

Scheme 1. Schematic for the synthesis of TPU/BP-MXene@PDA composite.

Fig. 1. SEM images of (a) MAX and (b) MXene after etching; (c) XRD patterns of MAX powders and MXene nanosheets; (d) TEM and (e) AFM micrographs of MXene, (f) corresponding height curves of MXene; (g) TEM and (h) AFM micrographs of BP nanosheets, (i) corresponding height curves of BP nanosheets.

Fig. 2. (a) XRD patterns, (b) Raman spectra, (c) FTIR spectra of MXene, BP, and BP1-MXene2@PDA; (d) XPS survey spectra of BP1-MXene2@PDA; the high-resolution (e) N 1s, (f) O 1s, (g) P 2p, and (h) Ti 2p XPS spectra of the BP1-MXene2@PDA; (i) TGA curves of MXene, BP, and all BP-MXene@PDA nanohybrids.

Fig. 3. SEM images of (a) BP nanosheets and (b) MXene nanosheets, (c) low- and (d) high-magnification SEM images of BP1-MXene2@PDA nanohybrids, and (e) corresponding elemental mapping images of C, N, P, O, Ti, and BP1-MXene2@PDA, respectively.

Fig. 4. (a) XRD patterns of the TPU, TM, TB, and TBM-1; (b) TEM image of TBM-1 composites.

Fig. 5. The mechanical properties of TPU and its composites: (a) stress-strain curve, (b) tensile strength and tensile strain.

Fig. 6. SEM images of the fractured surface of (a1, a2) pure TPU, (b1, b2) TM, (c1, c2) TB, and (d1, d2) TBM-1 following the tensile strength test.

Fig. 7. (a) TG and (b) DTG curves of pure TPU and its composites under nitrogen atmosphere.

Fig. 8. (a) HRR, (b) THR, (c) SPR, (d) TSP, (e) CO, and (f) CO2 vs. time curves of TPU and its composites.

Fig. 9. FTIR spectra of (a) TPU, (b) TM, (c) TB, and (d) TBM-1 at different pyrolysis temperatures.

Fig. 10. SEM images of the external and interior residues for pure TPU (a1, a2), TM (b1, b2), TB (c1, c2), and TBM-1 (d1, d2).

Fig. 11. Raman spectra of (a) pure TPU, (b) TM, (c) TB, (d) TBM-1, (e) TBM-2, and (f) TBM-3 residues.

Fig. 12. (a) XPS survey spectra for the residues; (b) the high-resolution O 1s XPS spectrum of TBM-1; the high-resolution P 2p XPS spectra of (c) TB and (d) TBM-1; the high-resolution Ti 2p XPS spectra of (e) TM and (f) TBM-1.

Fig. 13. (a) FTIR spectra and (b) XRD patterns of TBM-1 treated at different temperatures for 15 min.

Fig. 14. Trend diagram of Ti content in bottom and surface layer of TM and TBM-1 after treatment at different temperatures for 15 min.

Fig. 15. Cross-section SEM images of (a) pure TPU and (b) TBM-1 treated at different temperatures (treating time: ～15 min).

Scheme 2. The proposed flame-retardant mechanism for TPU/BP-MXene@PDA in TPU.

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