基于T1-T2*弛豫相关的聚氨酯橡胶相态结构和动力学特征

doi:10.11938/cjmr20223007

摘要/Abstract

摘要：

磁共振技术具有非破坏性、对高分子链运动敏感等特点，是一种能够在分子水平上表征高分子系统相态结构和动力学特征的常用技术．本文利用T₁-T₂^*弛豫相关研究了聚氨酯橡胶的相态结构和分子动力学特征，并用高斯衰减和指数衰减模型分析了聚氨酯橡胶的T₁-T₂^*数据．聚氨酯橡胶的T₁-T₂^*谱显示了三种类型的信号：晶体氢组分的T₂^*最短，过渡相氢组分具有中等的T₂^*，非晶体氢组分的T₂^*最长；但这三种氢组分表现出相近的T₁，且T₁随着聚氨酯橡胶硬度的增加或温度的降低而逐渐降低．三种氢组分的磁共振信号强度随聚氨酯橡胶的硬度和温度的变化而变化．随着聚氨酯橡胶硬度的增加，晶体氢组分含量增加，非晶体氢组分和过渡相氢组分的含量降低；随着温度的增加，晶体氢组分含量减少，过渡相氢组分含量保持不变，而非晶体氢组分含量增加．另外，聚氨酯橡胶的硬软比随温度的升高而降低．这些结果表明T₁-T₂^*弛豫相关可用于聚氨酯橡胶的相态结构和动力学评价．

关键词: 核磁共振, T₁-T₂^*弛豫相关, 聚氨酯橡胶, 相态结构, 动力学特征

Abstract:

Nuclear magnetic resonance (NMR) is a non-destructive technique that can reveal the phase structure and dynamics of polymers at the molecular level. It is sensitive to polymer chain mobility and requires minimal special sample preparation. We investigated the phase structure and molecular dynamics of polyurethane rubber (PUR) based on the T₁-T₂^* relaxation correlation spectra, and analyzed the T₁-T₂^* data by multi modal decay. The T₁-T₂^* spectra showed three types of signals: rigid ¹H with the shortest T₂^* value, interphase ¹H with an intermediate T₂^* value, and mobile-amorphous ¹H with the longest T₂^* value. The three ¹H components exhibit the similar T₁ values in PUR, which decreased with increasing hardness or decreasing temperature. The integrals of these signals depend on the durometer hardness and temperature for PUR. They increase for the rigid phase but reduce for mobile-amorphous phase and interphase with an increase of PUR durometer hardness. The rigid ¹H component decreased and the mobile-amorphous ¹H component increased with increasing temperature, while the interphase ¹H component remained constant. In addition, the hard/soft ratio decreased with increasing temperature for PUR systems. These results indicated that T₁-T₂^* spectra can be used to characterize phase structure and dynamics of PUR.

Key words: nuclear magnetic resonance, T₁-T₂^* relaxation correlation, polyurethane rubber, phase structure, dynamics

中图分类号:

O482.53

郭江峰,MACMILLAN Bryce,BALCOM Bruce. 基于T₁-T₂^*弛豫相关的聚氨酯橡胶相态结构和动力学特征[J]. 波谱学杂志, 2023, 40(2): 111-121.

GUO Jiangfeng,MACMILLAN Bryce,BALCOM Bruce. Insights into the Phase Structure and Dynamics of Polyurethane Rubber Using T₁-T₂^*Relaxation Correlation[J]. Chinese Journal of Magnetic Resonance, 2023, 40(2): 111-121.

图/表 9

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PUR样品	温度T/℃	90?脉冲的宽度/μs
40A	0	12.0
80A	0	11.9
75D	0	11.3
75D	20	10.9
75D	40	10.6
75D	60	9.8
75D	80	9.9

PUR样品	信号I			信号II			信号III			总信号强度
PUR样品	T₁/ms	T₂^*/μs	信号强度	T₁/ms	T₂^*/μs	信号强度	T₁/ms	T₂^*/μs	信号强度	总信号强度
40A	360	18	2.60×10⁵	360	39	7.40×10⁵	323	121	3.08×10⁵	1.31×10⁶
80A	323	20	4.03×10⁵	335	38	6.81×10⁵	301	106	2.20×10⁵	1.30×10⁶
75D	217	20	1.07×10⁶	234	46	2.88×10⁵	225	167	1.61×10⁵	1.52×10⁶

温度/℃	信号I			信号II			信号III			总信号强度
温度/℃	T₁/ms	T₂^*/μs	信号强度	T₁/ms	T₂^*/μs	信号强度	T₁/ms	T₂^*/μs	信号强度	总信号强度
0	217	20	1.07×10⁶	234	46	2.88×10⁵	225	167	1.61×10⁵	1.52×10⁶
20	217	20	8.81×10⁵	217	51	3.06×10⁵	217	202	2.69×10⁵	1.46×10⁶
40	242	21	7.34×10⁵	242	50	2.83×10⁵	242	219	3.71×10⁵	1.39×10⁶
60	280	21	6.04×10⁵	290	52	2.62×10⁵	280	245	4.38×10⁵	1.30×10⁶
80	355	21	4.98×10⁵	355	55	2.46×10⁵	355	258	4.69×10⁵	1.21×10⁶

基于T₁-T₂^*弛豫相关的聚氨酯橡胶相态结构和动力学特征

Insights into the Phase Structure and Dynamics of Polyurethane Rubber Using T₁-T₂^*Relaxation Correlation

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