Citation: Yong-jin Peng, Chen-ting Cai, Rong-chun Zhang, Tie-hong Chen, Ping-chuan Sun, Bao-hui Li, Xiao-liang Wang, Gi Xue, An-Chang Shi. Probing the Two-stage Transition upon Crossing the Glass Transition of Polystyrene by Solid-state NMR[J]. Chinese Journal of Polymer Science, ;2016, 34(4): 446-456. doi: 10.1007/s10118-016-1762-z shu

Probing the Two-stage Transition upon Crossing the Glass Transition of Polystyrene by Solid-state NMR

1.
School of Physics, Nankai University, Tianjin 300071, China
2.
Key Laboratory of Functional Polymer Materials of Ministry of Education and College of Chemistry, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300071, China
3.
Department of Polymer Science and Engineering, The School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China
4.
Department of Physics and Astronomy, McMaster University, Hamilton, Ontario L8S 4M1, Canada

Received Date: 16 October 2015
Revised Date: 29 November 2015

Fund Project: This work was financially supported by the National Science Fund for Distinguished Young Scholars (No. 20825416), and the National Natural Science Foundation of China (No. 21374051), 973 program (No. 2012CB821503), PCSIRT (No. IRT1257) and CERS-1-61. A.C.S. acknowledges the support of the Natural Science and Engineering Council (NSERC) of Canada.

A two-stage transition upon crossing the glass transition of polystyrene with increasing temperature was precisely determined and interpreted by using solid-state nuclear magnetic resonance (SSNMR), 1H-1H dipolar couplings based double quantum-filtered (DQF) and dipolar filter (DF) experiments and 13C chemical shift anisotropy (CSA) based centerband-only detection of exchange (CODEX) experiment are used to fully characterize the time scale of molecular motions during the glass transition. While differential scanning calorimetry (DSC) and CODEX experiment predicted the first stage of glass transiton, DQF and DF experiments provided the evidence for the second stage transition during which the time scale of molecular motions changed from very slow (tms) to very fast (ts). The first stage of glass transition begins with the occurrence of remarkable slow re-orientation motions of the polymer backbone segments and ends when the degree of slow motion reaches maximum. The onset and endpoint of the conventional calorimetric glass transition of polystyrene can be quantitatively determined at the molecular level by SSNMR. In the second stage, a subsequent dramatic transition associated with the melting of the glassy components was observed. In this stage liquid-like NMR signals appeared and rapidly increased in intensity after a characteristic temperature Tf (~1.1Tg). The signals associated with the glassy components completely disappeared at another characteristic temperature Tc (~1.2Tg).
- Glass transition,
- Polystyrene,
- Heterogeneous dynamics,
- Solid-state NMR
1. [1]
2. [2]
3. [3]
4. [4]
5. [5]
6. [6]
7. [7]
8. [8]
9. [9]
10. [10]
11. [11]
12. [12]
13. [13]
14. [14]
15. [15]
16. [16]
17. [17]
18. [18]
19. [19]
20. [20]
21. [21]
22. [22]
23. [23]
24. [24]
25. [25]
26. [26]
27. [27]
28. [28]
29. [29]
30. [30]
31. [31]
32. [32]
33. [33]
34. [34]
35. [35]
36. [36]
37. [37]
38. [38]
39. [39]
40. [40]
41. [41]
42. [42]
43. [43]
44. [44]
45. [45]
46. [46]
47. [47]
48. [48]
49. [49]
50. [50]
51. [51]
52. [52]
53. [53]
54. [54]
55. [55]
56. [56]
57. [57]
58. [58]
59. [59]
60. [60]
61. [61]
62. [62]
63. [63]
64. [64]
65. [65]
66. [66]
67. [67]
68. [68]
69. [69]
70. [70]
71. [71]
72. [72]
73. [73]
74. [74]
75. [75]
76. [76]
77. [77]
78. [78]
79. [79]
80. [80]
81. [81]
82. [82]
83. [83]
84. [84]
85. [85]
86. [86]
87. [87]
88. [88]
89. [89]
90. [90]
91. [91]
92. [92]
93. [93]
94. [94]
95. [95]
96. [96]
97. [97]
98. [98]
99. [99]
100. [100]
101. [101]
102. [102]
103. [103]
104. [104]
105. [105]
106. [106]
107. [107]
108. [108]
109. [109]
110. [110]
111. [111]
112. [112]
113. [113]
114. [114]
115. [115]
116. [116]
117. [117]
118. [118]
119. [119]
120. [120]
121. [121]
122. [122]
123. [123]
124. [124]
125. [125]
126. [126]
127. [127]
128. [128]
129. [129]
130. [130]
131. [131]
132. [132]
133. [133]
134. [134]
135. [135]
136. [136]
137. [137]
138. [138]
139. [139]
140. [140]
141. [141]
142. [142]
143. [143]
144. [144]
145. [145]
146. [146]
147. [147]
148. [148]
149. [149]
150. [150]
151. [151]
152. [152]
153. [153]
154. [154]
155. [155]
156. [156]
157. [157]
1. [1]
  Xinzhi Ding , Chong Liu , Jing Niu , Nan Chen , Shutao Xu , Yingxu Wei , Zhongmin Liu . Solid-state NMR study of the stability of MOR framework aluminum. Chinese Journal of Structural Chemistry, 2024, 43(4): 100247-100247. doi: 10.1016/j.cjsc.2024.100247
2. [2]
  Huixin Chen , Chen Zhao , Hongjun Yue , Guiming Zhong , Xiang Han , Liang Yin , Ding Chen . Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109650-. doi: 10.1016/j.cclet.2024.109650
3. [3]
  Biao Fang , Runwei Mo . PVDF-based solid-state battery. Chinese Journal of Structural Chemistry, 2024, 43(8): 100347-100347. doi: 10.1016/j.cjsc.2024.100347
4. [4]
  Tianyi Hou , Yunhui Huang , Henghui Xu . Interfacial engineering for advanced solid-state Li-metal batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100313-100313. doi: 10.1016/j.cjsc.2024.100313
5. [5]
  Mengjia Luo , Yi Qiu , Zhengyang Zhou . Exploring temperature-driven phase dynamics of phosphate: The periodic to incommensurately modulated long-range ordered phase transition in CsCdPO4. Chinese Journal of Structural Chemistry, 2025, 44(1): 100446-100446. doi: 10.1016/j.cjsc.2024.100446
6. [6]
  Peng Jia , Yunna Guo , Dongliang Chen , Xuedong Zhang , Jingming Yao , Jianguo Lu , Liqiang Zhang . In-situ imaging electrocatalysis in a solid-state Li-O₂ battery with CuSe nanosheets as air cathode. Chinese Chemical Letters, 2024, 35(5): 108624-. doi: 10.1016/j.cclet.2023.108624
7. [7]
  Qianqian Song , Yunting Zhang , Jianli Liang , Si Liu , Jian Zhu , Xingbin Yan . Boron nitride nanofibers enhanced composite PEO-based solid-state polymer electrolytes for lithium metal batteries. Chinese Chemical Letters, 2024, 35(6): 108797-. doi: 10.1016/j.cclet.2023.108797
8. [8]
  Chaochao Wei , Ru Wang , Zhongkai Wu , Qiyue Luo , Ziling Jiang , Liang Ming , Jie Yang , Liping Wang , Chuang Yu . Revealing the size effect of FeS₂ on solid-state battery performances at different operating temperatures. Chinese Chemical Letters, 2024, 35(6): 108717-. doi: 10.1016/j.cclet.2023.108717
9. [9]
  Caixia Li , Yi Qiu , Yufeng Zhao , Wuliang Feng . Self assembled electron blocking and lithiophilic interface towards dendrite-free solid-state lithium battery. Chinese Chemical Letters, 2024, 35(4): 108846-. doi: 10.1016/j.cclet.2023.108846
10. [10]
  Ting WANG , Peipei ZHANG , Shuqin LIU , Ruihong WANG , Jianjun ZHANG . A Bi-CP-based solid-state thin-film sensor: Preparation and luminescence sensing for bioamine vapors. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1615-1621. doi: 10.11862/CJIC.20240134
11. [11]
  Ying Li , Yanjun Xu , Xingqi Han , Di Han , Xuesong Wu , Xinlong Wang , Zhongmin Su . A new metal–organic rotaxane framework for enhanced ion conductivity of solid-state electrolyte in lithium-metal batteries. Chinese Chemical Letters, 2024, 35(9): 109189-. doi: 10.1016/j.cclet.2023.109189
12. [12]
  Yang Deng , Yitao Ouyang , Chao Han . Constriction-susceptible makes fast cycling of lithium metal in solid-state batteries: Silicon as an example. Chinese Journal of Structural Chemistry, 2024, 43(7): 100276-100276. doi: 10.1016/j.cjsc.2024.100276
13. [13]
  Dong Sui , Jiayi Liu . Constriction-susceptible lithium support for fast cycling of solid-state lithium metal battery. Chinese Chemical Letters, 2025, 36(2): 110417-. doi: 10.1016/j.cclet.2024.110417
14. [14]
  Linhui Liu , Wuwan Xiong , Mingli Fu , Junliang Wu , Zhenguo Li , Daiqi Ye , Peirong Chen . Efficient NO_x abatement by passive adsorption over a Pd-SAPO-34 catalyst prepared by solid-state ion exchange. Chinese Chemical Letters, 2024, 35(4): 108870-. doi: 10.1016/j.cclet.2023.108870
15. [15]
  Shuai Li , Liuting Zhang , Fuying Wu , Yiqun Jiang , Xuebin Yu . Efficient catalysis of FeNiCu-based multi-site alloys on magnesium-hydride for solid-state hydrogen storage. Chinese Chemical Letters, 2025, 36(1): 109566-. doi: 10.1016/j.cclet.2024.109566
16. [16]
  Xin Li , Ling Zhang , Yunyan Fan , Shaojing Lin , Yong Lin , Yongsheng Ying , Meijiao Hu , Haiying Gao , Xianri Xu , Zhongbiao Xia , Xinchuan Lin , Junjie Lu , Xiang Han . Carbon interconnected microsized Si film toward high energy room temperature solid-state lithium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109776-. doi: 10.1016/j.cclet.2024.109776
17. [17]
  Ziling Jiang , Shaoqing Chen , Chaochao Wei , Ziqi Zhang , Zhongkai Wu , Qiyue Luo , Liang Ming , Long Zhang , Chuang Yu . Enabling superior electrochemical performance of NCA cathode in Li_5.5PS_4.5Cl_1.5-based solid-state batteries with a dual-electrolyte layer. Chinese Chemical Letters, 2024, 35(4): 108561-. doi: 10.1016/j.cclet.2023.108561
18. [18]
  Mengxiang Zhu , Tao Ding , Yunzhang Li , Yuanjie Peng , Ruiping Liu , Quan Zou , Leilei Yang , Shenglei Sun , Pin Zhou , Guosheng Shi , Dongting Yue . Graphene controlled solid-state growth of oxygen vacancies riched V₂O₅ catalyst to highly activate Fenton-like reaction. Chinese Chemical Letters, 2024, 35(12): 109833-. doi: 10.1016/j.cclet.2024.109833
19. [19]
  Chenghao Ge , Peng Wang , Pei Yuan , Tai Wu , Rongjun Zhao , Rong Huang , Lin Xie , Yong Hua . Tuning hot carrier transfer dynamics by perovskite surface modification. Chinese Chemical Letters, 2024, 35(10): 109352-. doi: 10.1016/j.cclet.2023.109352
20. [20]
  Zizhuo Liang , Fuming Du , Ning Zhao , Xiangxin Guo . Revealing the reason for the unsuccessful fabrication of Li3Zr2Si2PO12 by solid state reaction. Chinese Journal of Structural Chemistry, 2023, 42(11): 100108-100108. doi: 10.1016/j.cjsc.2023.100108

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(765)
HTML views(40)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142