\[\lg a_T = -\frac{C_1(T - T_\text{ref})}{C_2 + T - T_\text{ref}},\qquad C_1 \approx 17.44,\ C_2 \approx 51.6\ \mathrm K\ (T_\text{ref} = T_g)\]
含义Meaning
玻璃化温度以上(Tg 至约 Tg + 100 K)高分子松弛时间、黏度随温度的变化,是时–温叠加原理中移动因子 \(a_T\) 的经验表达(1955)。
Temperature dependence of relaxation times and viscosity above Tg (to about Tg + 100 K): the shift factor a_T of time–temperature superposition (1955).
符号说明Symbols
| 符号Symbol | 含义 Meaning | 单位 Unit |
|---|---|---|
| \(a_T\) | 移动因子 τ(T)/τ(T_ref)shift factor τ(T)/τ(T_ref) | 1 |
| \(C_1, C_2\) | “通用”常数‘universal’ constants | 1, K |
推导Derivation
多利特尔黏度方程 \(\ln\eta = A + B/f\),f 为自由体积分数。
Doolittle: \(\ln\eta = A + B/f\), f the free-volume fraction.
假设 f 在 Tg 以上随温度线性增加:\(f = f_g + \alpha_f(T - T_g)\)。
Assume \(f = f_g + \alpha_f(T - T_g)\).
两温度相减整理即得 WLF 形式,\(C_1 = B/(2.303f_g)\),\(C_2 = f_g/\alpha_f\)。
Subtracting gives WLF with \(C_1 = B/2.303f_g\), \(C_2 = f_g/\alpha_f\).
适用条件与局限Assumptions & limitations
只在 Tg < T < Tg + 100 K 适用;更高温度用阿伦尼乌斯型。“通用”常数只是平均值。
Valid for Tg < T < Tg + 100 K; the ‘universal’ constants are averages.