Conformational Disorder Within the Crystalline Region of Silica-Filled Polydimethylsiloxane: A Solid-State NMR Study

Yu-Qi Xiong; Chang-Lin Li; Ai Lu; Liang-Bin Li; Wei Chen

doi:10.1007/s10118-024-3164-y

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Conformational Disorder Within the Crystalline Region of Silica-Filled Polydimethylsiloxane: A Solid-State NMR Study

RESEARCH ARTICLE | Updated：2024-11-04

- Conformational Disorder Within the Crystalline Region of Silica-Filled Polydimethylsiloxane: A Solid-State NMR Study
- Conformational Disorder Within the Crystalline Region of Silica-Filled Polydimethylsiloxane: A Solid-State NMR Study
- 高分子科学（英文版） 2024年42卷第11期页码：1780-1792
- Affiliations：
  
  a.National Synchrotron Radiation Laboratory, Anhui Provincial Engineering Laboratory of Advanced Functional Polymer Film, CAS Key Laboratory of Soft Matter Chemistry, University of Science and Technology of China, Hefei 230026, China
  b.Department of Accelerator Science and Engineering Physics, School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230026, China
  c.Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, China
- Author bio：
  
  lbli@ustc.edu.cn (L.B.L.)
  wc003@ustc.edu.cn (W.C.)
- Funds：
  
  This work was financially supported by NSAF Joint Fund of China (No. U2030203), the National Natural Science Foundation of China (Nos. 51973207 and 51903230) and the experimental assistance from Shanghai Synchrotron Radiation Facility (SSRF) for WAXS measurement are greatly appreciated.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-024-3164-y.
- DOI：10.1007/s10118-024-3164-y
  中图分类号：
- 收稿：2024-04-07，
  
  修回：2024-05-06，
  
  录用：2024-05-14，
  
  网络首发：2024-08-20，
  
  纸质出版：2024-11-30
- Accepted：
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Xiong, Y. Q.; Li, C. L.; Lu, A.; Li, L. B.; Chen, W. Conformational disorder within the crystalline region of silica-filled polydimethylsiloxane: a solid-state NMR study. Chinese J. Polym. Sci. 2024, 42, 1780–1792

Yu-Qi Xiong, Chang-Lin Li, Ai Lu, et al. Conformational Disorder Within the Crystalline Region of Silica-Filled Polydimethylsiloxane: A Solid-State NMR Study[J]. Chinese Journal of Polymer Science, 2024, 42(11): 1780-1792.
Xiong, Y. Q.; Li, C. L.; Lu, A.; Li, L. B.; Chen, W. Conformational disorder within the crystalline region of silica-filled polydimethylsiloxane: a solid-state NMR study. Chinese J. Polym. Sci. 2024, 42, 1780–1792 DOI： 10.1007/s10118-024-3164-y.

Yu-Qi Xiong, Chang-Lin Li, Ai Lu, et al. Conformational Disorder Within the Crystalline Region of Silica-Filled Polydimethylsiloxane: A Solid-State NMR Study[J]. Chinese Journal of Polymer Science, 2024, 42(11): 1780-1792. DOI： 10.1007/s10118-024-3164-y.

摘要

Using solid-state NMR

synchrotron WAXS

and TMDSC techniques

silica filler-induced crystalline chain conformational disorder in silicone rubber composites was first discovered

elucidating the impact of fillers on crystalline chain conformational order.

Abstract

The crystallization behavior of silica-filled polydimethylsiloxane (PDMS) was investigated in detail by

H solid-state nuclear magnetic resonance (

H SS-NMR) in combination with synchrotron radiation wide-angle X-ray scattering (WAXS)

and temperature-modulated differential scanning calorimetry (TMDSC) techniques. For neat PDMS

no apparent difference is observed for the crystallinity characterized by

H SS-NMR and WAXS at low-temperature regions. However

upon filler addition

a 15%−35% lower difference in crystallinity is observed measured by

H SS-NMR compared to WAXS. The origin of such mismatch was explored through multi-component structural

dynamics

and chain-order analysis of PDMS samples with different filler fractions. The 1D integrated WAXS results of PDMS with different filler fractions at different temperatures show that the packing structure as well as crystal size basically remain unchanged

but as the filler fraction increases from 0 phr to 60 phr

the rigid component’s dynamics order parameter

obtained by

H SS-NMR decreases from 0.70 to 0.55. The filler fraction-dependent crystallinity calculated based on

was compared with experimental values

revealing a behavior of decreasing order in the crystalline region. Combining with the results of accelerated chain dynamics in crystalline region as reflected by

values

the molecular origin is attributed to the formation of CONDIS crystals

whose conformational order is lost but the position and orientation orders are kept. Such hypothesis is further supported by the TMDSC results

where

as the filler fraction increases from 0 phr to 60 phr

the melting range widens from 8.77 K to 14.56 K

representing a growth of 166%. In addition to previous reports related to the condition for forming CONDIS mesophase

i.e.

temperature

pressure

and stretching

the nano-sized filler could also introduce the local conformational disorder for chain packing.

关键词

Keywords

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